Pyridine-acetyl sulfonamide compound, polyester prepared from pyridine-acetyl sulfonamide compound, and preparation method and application thereof

Abstract

The present invention relates to the technical field of polyester preparation, and discloses a pyridine-acetyl sulfonamide compound, the pyridine-acetyl sulfonamide compound has a structure represented by a formula (I): in the formula (I), R1 and R2 are independently selected from dimethylamino, pyrrolidinyl, hydrogen, and C1-C10 substituted or unsubstituted straight chain or branched chain alkyl; and R3 and R4 are respectively and independently selected from hydrogen and substituted or unsubstituted straight chain or branched chain alkyl of C1-C10. The pyridine-acetyl sulfonamide compound can be used as a catalyst for preparing polyester, a polymerization reaction is catalyzed under the action of hydrogen bonds, ring-opening polymerization with controllable activity is achieved, and compared with reported catalysts, the catalyst has the advantages of being high in catalytic efficiency, mild in catalytic condition, free of metal residues and the like, and is suitable for industrial production. Important application prospects are realized in the field of biological medicines. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of polyester preparation, in particular to a pyridine-acetylsulfonamide compound, a polyester prepared therefrom and a preparation method thereof. Background Art

[0002] Aliphatic polyesters are an important class of polymer materials with good biocompatibility and biodegradability. They have broad application prospects in the biomedical field and have been widely used in absorbable surgical sutures, drug carriers, tissue engineering scaffolds, etc.

[0003] The methods for synthesizing aliphatic polyesters mainly include polycondensation of fatty acids and fatty alcohols and ring-opening polymerization of cyclic lactones. The polycondensation of fatty acids and fatty alcohols has the disadvantages of harsh reaction conditions, inability to accurately control the molecular weight of the product, low molecular weight of the prepared product, wide molecular weight distribution of the product, and the generation of small molecular weight byproducts. Catalytic ring-opening polymerization is currently a hot topic in the research of preparing synthetic aliphatic polyesters, and its catalytic system includes metal-ligand or metal alkane compound catalysis, enzyme catalysis and organic small molecule catalysis. Among them, the metals in the metal-ligand include metals such as iron, cobalt, aluminum, and zinc, and the metal alkane compounds include zinc isopropoxide, alkyl aluminum, aryl aluminum, stannous octoate, and rare earth alkoxides. The residues of these catalysts in the polymer have more or less potential toxicity to human cells, which limits the application of the polymer. Enzyme catalysis has high catalytic activity, but the catalysis is specific and has a catalytic effect only on a certain lactone, and has poor universality for monomer types. Compared with the first two catalytic polymerization systems, organic catalytic lactone ring-opening polymerization has the advantages of mild reaction conditions, controllable polymerization reaction, narrow molecular weight distribution, etc., and the produced polymer does not contain metals. As a biocompatible material, it can be used in food packaging or drug release or delivery. However, the current organic catalytic lactone ring-opening polymerization reaction has the problems of poor catalytic activity and low conversion rate. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of poor catalytic activity and low conversion rate in the prior art organic catalytic lactone ring-opening polymerization reaction, and to provide a pyridine-acetylsulfonamide compound, a polyester prepared using the same, and a preparation method thereof. The pyridine-acetylsulfonamide compound has the characteristics of high catalytic activity and no metal when used as a polyester catalyst; the conversion rate of the cyclic monomer is high, and the obtained polymer has the characteristics of high yield and narrow molecular weight distribution.

[0005] In order to achieve the above object, the first aspect of the present invention provides a pyridine-acetyl sulfonamide compound, wherein the pyridine-acetyl sulfonamide compound has a structure shown in formula (I):

[0006]

[0007] In formula (I), R 1 and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

[0008] The second aspect of the present invention provides a method for preparing a pyridine-acetylsulfonamide compound, the method comprising: reacting a pyridine derivative with an acetylsulfonamide compound to obtain a pyridine-acetylsulfonamide compound; wherein the pyridine-acetylsulfonamide compound has a structure shown in formula (I); the pyridine derivative has a structure shown in formula (II); the acetylsulfonamide compound has a structure shown in formula (III);

[0009]

[0010] Among them, R 1 and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

[0011] The third aspect of the present invention provides a pyridine-acetylsulfonamide compound prepared by the aforementioned preparation method.

[0012] The fourth aspect of the present invention provides use of the aforementioned pyridine-acetylsulfonamide compound in the preparation of polyester.

[0013] A fifth aspect of the present invention provides a method for preparing polyester, the method comprising: subjecting a cyclic monomer to a ring-opening polymerization reaction in the presence of a catalyst to obtain polyester; wherein the catalyst is the aforementioned pyridine-acetylsulfonamide compound.

[0014] The sixth aspect of the present invention provides a polyester obtained by the aforementioned preparation method, wherein the polyester has a number average molecular weight of 1000-100000 g / mol, a molecular weight distribution coefficient of 1-2, and a metal content of 0.

[0015] A seventh aspect of the present invention provides use of the aforementioned polyester in biomedical materials or food packaging materials.

[0016] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0017] The pyridine-acetylsulfonamide compound of the invention is prepared by using industrially cheap and easily available pyridine derivatives and food additive acetylsulfonamide compounds as raw materials. The preparation method is simple, easy to operate and has a wide range of raw material sources.

[0018] The pyridine-acetylsulfonamide compound of the present invention can be used as a catalyst for preparing polyester, catalyzes polymerization reactions through the action of hydrogen bonds, and realizes active controllable ring-opening polymerization. Compared with previously reported catalysts, the catalyst has the characteristics of high catalytic efficiency, mild catalytic conditions, and no metal residue, and has important application prospects in the field of biomedicine.

[0019] The polyester prepared by using the pyridine-acetylsulfonamide compound of the present invention as a catalyst has a narrow molecular weight distribution index, a high product yield, no monomer residue, and a snow-white color; and the present invention utilizes an organic hydrogen bond catalyst to synthesize a variety of biodegradable high molecular weight polymers.

[0020] Compared with the existing synthesis process, the present invention has the characteristics of being green and non-toxic, having good biocompatibility, having a new structure, having a simple synthesis process and having a high yield, etc., and meets the requirements of the biomedical and microelectronic fields for materials and the requirements for simply, gently and efficiently synthesizing polymers with precise molecular weights. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The compound 20 prepared in Preparation Example 1 of the present invention 1 H NMR spectra;

[0022] Figure 2 The polylactide (PLA) prepared in Example 5 of the present invention 1 H NMR spectra;

[0023] Figure 3 The polytrimethylene carbonate (PTMC) prepared in Example 7 of the present invention is 1 HNMR spectrum. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] The first aspect of the present invention provides a pyridine-acetylsulfonamide compound, wherein the pyridine-acetylsulfonamide compound has a structure shown in formula (I):

[0026]

[0027] In formula (I), R 1 and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

[0028] In the present invention, C1-C 10 In the substituted or unsubstituted straight-chain or branched alkyl group, the substituents include, but are not limited to, one or more of the following groups: halogen, hydroxyl, phenyl and substituted phenyl.

[0029] In the present invention, R 2 Located in R 1 The ortho and / or meta positions, i.e., R 2 Can be located in R 1 The adjacent position, R 2 Can be located in R 1 The meta position, R 2 It can also be located at R 1 The ortho and meta positions can be adjusted according to specific needs.

[0030] In some embodiments of the present invention, R 1 is selected from dimethylamino, pyrrolidinyl, tert-butyl or hydrogen; R 2 is selected from hydrogen, methyl, ethyl, butyl, isopropyl or tert-butyl; R 4 is selected from hydrogen or methylphenyl, R 3 is selected from hydrogen, methyl, butyl or phenyl.

[0031] In some embodiments of the present invention, the pyridine-acetylsulfonamide compound has at least one of the structures shown in Formula I-1 to Formula I-9:

[0032]

[0033] The second aspect of the present invention provides a method for preparing a pyridine-acetylsulfonamide compound, the method comprising: reacting a pyridine derivative with an acetylsulfonamide compound to obtain a pyridine-acetylsulfonamide compound; wherein the pyridine-acetylsulfonamide compound has a structure shown in formula (I); the pyridine derivative has a structure shown in formula (II); the acetylsulfonamide compound has a structure shown in formula (III);

[0034]

[0035] Among them, R 1and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

[0036] In the present invention, C1-C 10 In the substituted or unsubstituted straight-chain or branched alkyl group, the substituents include, but are not limited to, one or more of the following groups: halogen, hydroxyl, phenyl and substituted phenyl.

[0037] In the present invention, R 2 Located in R 1 The ortho and / or meta positions, i.e., R 2 Can be located in R 1 The adjacent position, R 2 Can be located in R 1 The meta position, R 2 It can also be located at R 1 The ortho and meta positions can be adjusted according to specific needs.

[0038] In some embodiments of the present invention, R 1 is selected from dimethylamino, pyrrolidinyl, tert-butyl or hydrogen; R 2 is selected from hydrogen, methyl, ethyl, butyl, isopropyl or tert-butyl; R 4 is selected from hydrogen or methylphenyl, R 3 is selected from hydrogen, methyl, butyl or phenyl.

[0039] In some preferred embodiments of the present invention, the pyridine derivative has at least one of the structures shown in Formula II-1 to Formula II-12:

[0040]

[0041]

[0042] In some preferred embodiments of the present invention, the acetylsulfonamide compound has at least one of the structures shown in Formula III-1 to Formula III-6:

[0043]

[0044] In some preferred embodiments of the present invention, the pyridine-acetylsulfonamide compound has at least one of the structures shown in Formula I-1 to Formula I-9:

[0045]

[0046] In some embodiments of the present invention, the molar ratio of the pyridine derivative to the acetylsulfonamide compound is 0.5-2:1.

[0047] In the present invention, the reaction is an organic catalytic ring-opening polymerization reaction.

[0048] In some embodiments of the present invention, the reaction temperature is 25°C-80°C, and the reaction time is 6-24h.

[0049] In some embodiments of the present invention, the reaction is carried out in a solvent, and the solvent is at least one of tetrahydrofuran, dichloromethane, chloroform and toluene.

[0050] The third aspect of the present invention provides a pyridine-acetylsulfonamide compound prepared by the aforementioned preparation method.

[0051] In some embodiments of the present invention, the pyridine-acetylsulfonamide compound has one of the structures shown in Formula I-1 to Formula I-9:

[0052]

[0053]

[0054] The fourth aspect of the present invention provides use of the aforementioned pyridine-acetylsulfonamide compound in the preparation of polyester.

[0055] The present invention uses industrially cheap and readily available pyridine derivatives and food additive acetylsulfonamide compounds as raw materials to synthesize pyridine-acetylsulfonamide compounds, and the pyridine-acetylsulfonamide compounds can be used as catalysts for preparing polyesters. Compared with the existing catalytic system, the present invention has obvious advantages such as mildness, high efficiency, wide sources, simple synthesis, many types, wide range, no metal, stable structure, convenient use, easy control of polymerization process, etc. It has important application prospects in the field of biomedicine.

[0056] A fifth aspect of the present invention provides a method for preparing polyester, the method comprising: subjecting a cyclic monomer to a ring-opening polymerization reaction in the presence of a catalyst to obtain polyester; wherein the catalyst is the aforementioned pyridine-acetylsulfonamide compound.

[0057] The method of the present invention uses the aforementioned pyridine-acetylsulfonamide compound as a catalyst to catalyze the polymerization reaction through the action of hydrogen bonds. Compared with the catalysts reported previously, the catalyst has the characteristics of high catalytic efficiency and milder properties.

[0058] In some embodiments of the present invention, the cyclic monomer is a monomer having a structure represented by formula (IV) or a monomer having a structure represented by formula (V);

[0059]

[0060] In formula (IV), A is the general formula [-(CR1R2)-] n The structure shown, n is an integer of 2-10; R1 and R2 are each independently selected from hydrogen, C1-C5 substituted or unsubstituted straight chain or branched alkyl; X is selected from oxygen;

[0061] In formula (V), A and B are each independently a general formula [-(CR1R2)-] m In the structure shown, m is an integer of 2-10; R1 and R2 are each independently selected from hydrogen, C1-C5 substituted or unsubstituted straight chain or branched alkyl; and X is selected from oxygen.

[0062] In some embodiments of the present invention, the cyclic monomer is β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone or undecalactone.

[0063] The undecalactone in the present invention refers to macrocyclic undecalactone.

[0064] In some embodiments of the present invention, the cyclic monomer is glycolide, lactide, butyride, decide, decamide, O-carboxyanhydride (OCA) or N-carboxyanhydride (NCA).

[0065] The decalide in the present invention refers to macrocyclic decalide.

[0066] In the present invention, the conversion rate of the cyclic monomer is 90%-99%.

[0067] In some embodiments of the present invention, the catalyst is added in an amount of 0.05-10 mol % of the cyclic monomer.

[0068] In some embodiments of the present invention, the ring-opening polymerization reaction is carried out at a temperature of 80-140° C. and for a time of 0.2-24 h.

[0069] The invention adopts pyridine-acetylsulfonamide catalyzed ring-opening polymerization to prepare polyester in the presence or absence of solvent. The polyester includes but is not limited to polybutyrolactone, polyvalerolactone, polycaprolactone, polylactide, polyglycolide and polytrimethylene carbonate.

[0070] In the present invention, the ring-opening polymerization reaction is carried out in the presence of a solvent or in the absence of a solvent; when the polymerization is carried out in the presence of a solvent, the solvent includes but is not limited to: one or more of acetone, cyclohexanone, dioxane, tetrahydrofuran, benzene, toluene, xylene, dichloromethane, chloroform, tetrachloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and acetonitrile; preferably tetrahydrofuran, toluene, dichloromethane, chloroform or N,N-dimethylformamide.

[0071] In the present invention, the ring-opening polymerization reaction is carried out in the presence of an initiator or in the absence of an initiator; when the ring-opening polymerization reaction is carried out in the presence of an initiator, the initiator is but not limited to: one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, benzyl alcohol, phenylethyl alcohol, ethylene glycol, 5-hexen-1-ol and water.

[0072] In the present invention, the molar ratio of the initiator to the catalyst pyridine phenolate is 0.01-10:1.

[0073] In the present invention, the ring-opening polymerization reaction is completed under vacuum with a vacuum degree of 1-500 Pa; or under protective gas (inert gas, such as Ar) with a protective gas pressure of 100-101325 Pa.

[0074] In the solution before the ring-opening polymerization reaction, the initial reaction concentration of the cyclic monomer is 0.1 mol / L-100 mol / L; after the ring-opening polymerization reaction is completed, a terminator is added, and the terminator is triethylamine. After the terminator is added, a precipitation solvent is added or the precipitation solvent is directly added, and the precipitation solvent is methanol, ethanol, ether or n-hexane.

[0075] The sixth aspect of the present invention provides a polyester obtained by the aforementioned preparation method, wherein the polyester has a number average molecular weight of 1000-100000 g / mol, a molecular weight distribution coefficient of 1-2, and a metal content of 0.

[0076] With the pyridine-phenol compound of the present invention as a catalyst, the conversion rate of the cyclic monomer is high (90-99%), and the corresponding polyester prepared has a low dispersion index (PDI).

[0077] The catalyst prepared by the invention has controllable activity and no chain transesterification reaction. The polyester prepared by the catalyst has the characteristics of narrow molecular weight distribution index, high product yield, no monomer residue, snow-white color and the like.

[0078] The polyester obtained by the invention is a high molecular weight biodegradable material with a large molecular weight, a narrow molecular weight distribution and no metal impurities, and has important industrial application prospects and great commercial application potential in the fields of biomedicine and microelectronics.

[0079] A seventh aspect of the present invention provides use of the aforementioned polyester in biomedical materials or food packaging materials.

[0080] The polyester prepared by the method of the present invention can be used as a biomedical material or a food packaging material, especially a degradable food packaging material. For example, polycaprolactone (PCL) and polylactide (PLA) can be used as degradable surgical sutures, polycaprolactone can also be used for medical surgical splints, and polylactide can also be used as food packaging bags, straws, lunch boxes, etc.

[0081] The present invention is described in detail below by way of examples, but the protection scope of the present invention is not limited to the following description.

[0082] In the following examples and comparative examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are all conventional products that can be obtained through commercial channels.

[0083] The nuclear magnetic resonance hydrogen spectra involved in the following examples were measured using a Bruker AscendTM-400 nuclear magnetic resonance hydrogen spectrometer produced by Bruker Corporation, and the deuterated reagents used were deuterated chloroform (CDCl3) and deuterated dimethyl sulfoxide (DMSO-d6).

[0084] Preparation Example 1

[0085] The preparation method of the compound of the structure shown in formula I-2 specifically comprises the following steps:

[0086] (1) 5 g of the compound of formula III-1 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, the solid was recrystallized twice from ethyl acetate to produce needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0087] (2) Add the compound of formula II-7 (0.5 g, 4.09 mmol) and the acidified acesulfame potassium (0.667 g, 4.09 mmol) obtained in step (1) into a 100 mL round-bottom flask, use 20 mL THF as solvent, and react at 60°C overnight. After the reaction, remove the solvent by vacuum method, and recrystallize the product with methanol to form a hot saturated solution. Add 10 mL of n-hexane, and diffuse the solvent at room temperature for a period of time to produce white crystals to obtain the compound of formula I-2. The isolated yield is 80%. Figure 1 The product shown is 1 HNMR spectrum, from Figure 1 It can be seen that the catalyst has high purity.

[0088] Preparation Example 2

[0089] The method for preparing the compound of the structure shown in formula I-1 specifically comprises the following steps:

[0090] (1) 5 g of the compound of formula III-1 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, the solid was recrystallized twice from ethyl acetate to produce needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0091] (2) The compound of formula II-1 (0.43 g, 4.09 mmol) and the acidified acesulfame potassium obtained in step (1) (0.667 g, 4.09 mmol) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain the compound of formula I-1. The isolated yield was 81%.

[0092] Preparation Example 3

[0093] The preparation method of the compound of the structure shown in formula I-3 specifically comprises the following steps:

[0094] (1) 5 g of the compound of formula III-1 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, the solid was recrystallized twice from ethyl acetate to produce needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0095] (2) The compound of formula II-11 (4.09 mmol) and the acidified acesulfame potassium (4.09 mmol) obtained in step (1) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method. The product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-3. The isolated yield was 87%.

[0096] Preparation Example 4

[0097] The method for preparing the compound of the structure shown in formula I-4 specifically comprises the following steps:

[0098] (1) 5 g of the compound of formula III-2 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, the solid was recrystallized twice from ethyl acetate to produce needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0099] (2) The compound of formula II-2 (4.09 mmol) and the acidified acesulfame potassium obtained in step (1) (4.09 mmol) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-4. The isolated yield was 83%.

[0100] Preparation Example 5

[0101] The method for preparing the compound of the structure shown in formula I-5 specifically comprises the following steps:

[0102] (1) 5 g of the compound of formula III-3 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, it was recrystallized from ethyl acetate twice to generate needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0103] (2) The compound of formula II-8 (4.09 mmol) and the acidified acesulfame potassium (4.09 mmol) obtained in step (1) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-5. The isolated yield was 90%.

[0104] Preparation Example 6

[0105] The preparation method of the compound of the structure shown in Formula I-6 specifically comprises the following steps:

[0106] (1) 5 g of the compound of formula III-4 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, it was recrystallized from ethyl acetate twice to generate needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0107] (2) The compound of formula II-9 (4.09 mmol) and the acidified acesulfame potassium (4.09 mmol) obtained in step (1) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-6. The isolated yield was 90%.

[0108] Preparation Example 7

[0109] The preparation method of the compound of formula I-7 specifically comprises the following steps:

[0110] (1) 5 g of the compound of formula III-2 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, the solid was recrystallized twice from ethyl acetate to produce needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0111] (2) The compound of formula II-5 (4.09 mmol) and the acidified acesulfame potassium (4.09 mmol) obtained in step (1) were added to a 100 mL round-bottom flask, and 20 mL THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-7. The isolated yield was 90%.

[0112] Preparation Example 8

[0113] The preparation method of the compound of the structure shown in formula I-8 specifically comprises the following steps:

[0114] (1) 5 g of the compound of formula III-5 was dissolved in 10 mL of water, 6 mL of concentrated hydrochloric acid was added dropwise, and the mixture was stirred and extracted with 20 mL of ethyl acetate. The solvent was evaporated in the air to obtain a colorless solid. After the solvent was slowly evaporated in the air, it was recrystallized from ethyl acetate twice to generate needle-shaped colorless crystals to obtain acidified acesulfame potassium;

[0115] (2) The compound of formula II-12 (4.09 mmol) and the acidified acesulfame potassium (4.09 mmol) obtained in step (1) were added to a 100 mL round-bottom flask, and 20 mL of THF was used as solvent. The reaction was carried out at 60° C. overnight. After the reaction was completed, the solvent was removed by vacuum method, and the product was recrystallized from methanol to form a hot saturated solution. 10 mL of n-hexane was added, and the solvent was diffused at room temperature for a period of time to produce white crystals to obtain a compound of formula I-8. The isolated yield was 95%.

[0116] Preparation Comparative Example 1

[0117] The method of Preparation Example 1 is followed, except that the compound with the structure shown in Formula II-2 is replaced by chloropyridine to obtain a compound with the structure shown in the following Formula D-1.

[0118]

[0119] Example 1

[0120] In a 10mL reaction tube, add butyrolactone (0.3856g, 2.88mmol), benzyl alcohol (10μL, 0.096mmol), and the compound of the structure shown in formula I-2 (0.027g, 0.096mmol), and stir magnetically at 80℃ for 2h. After the reaction is completed, the crude product is dissolved in a small amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitates. Centrifugal separation gives 0.26g of a white solid, which is transferred to a vacuum drying oven for drying. The structure of the polymer is identified by NMR, and the molecular weight and dispersity of the polymer are determined by GPC. It has been determined that the conversion rate of butyrolactone is 92%, the number average molecular weight is 2700g / mol, and the molecular weight distribution coefficient is 1.29.

[0121] Example 2

[0122] In a 10mL reaction tube, add ε-caprolactone (0.3168mL, 2.88mmol), benzyl alcohol (10μL, 0.096mmol), and the compound of the structure shown in formula I-1 (0.023g, 0.096mmol), and stir magnetically at 100℃ for 3h. After the reaction is completed, the crude product is dissolved in a small amount of DCM and then added to a cold methanol solution, and a polymer precipitates. Centrifugal separation obtains 0.25g of a white solid, which is transferred to a vacuum drying oven for drying. The structure of the polymer is identified by NMR, and the molecular weight and dispersity of the polymer are determined by GPC. It has been determined that the conversion rate of ε-caprolactone is 95%, the number average molecular weight is 3600g / mol, and the molecular weight distribution coefficient is 1.33.

[0123] Example 3

[0124] In a 10mL reaction tube, valerolactone (0.288g, 2.88mmol), benzyl alcohol (10μL, 0.096mmol), and the compound of the structure shown in formula I-3 (0.030g, 0.096mmol) were added, and magnetic stirring was carried out at 90°C for 4h. After the reaction was completed, the crude product was dissolved in a small amount of DCM and then added to a cold methanol solution, and a polymer was precipitated. Centrifugation gave 0.22g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the molecular weight and dispersity of the polymer were determined by GPC. It was determined that the conversion rate of valerolactone was 95%, the number average molecular weight was 3000g / mol, and the molecular weight distribution coefficient was 1.24.

[0125] Example 4

[0126] In a 10mL reaction tube, glycolide (0.6682g, 5.76mmol), benzyl alcohol (10μL, 0.096mmol), and a compound of the structure shown in formula I-4 (0.026g, 0.096mmol) were added, and magnetic stirring was carried out at 140°C for 5h. After the reaction was completed, the crude product was dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitated. Centrifugation gave 0.47g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the molecular weight and dispersity of the polymer were determined by GPC. It was determined that the conversion rate of glycolide was 94%, the number average molecular weight was 6400g / mol, and the molecular weight distribution coefficient was 1.23.

[0127] Example 5

[0128] In a 10mL reaction tube, lactide (1.244g, 8.64mmol), benzyl alcohol (10μL, 0.096mmol), and the compound of the structure shown in formula I-5 (0.026g, 0.096mmol) were added, and magnetic stirring was performed at 140℃ for 6h. After the reaction, the crude product was dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitated. Centrifugation was performed to obtain 0.90g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the following was obtained: Figure 2 shown 1 H NMR spectrum, from Figure 2 It can be seen that the purity of lactide is high. The molecular weight and dispersion of the polymer are determined by GPC. It is determined that the conversion rate of lactide is 96%, the number average molecular weight is 12000 g / mol, and the molecular weight distribution coefficient is 1.29.

[0129] Example 6

[0130] In a 10mL reaction tube, carboxylic acid anhydride (0.415g, 5.76mmol), benzyl alcohol (10μL, 0.096mmol), and a compound of the structure shown in formula I-6 (0.028g, 0.096mmol) were added, and magnetic stirring was carried out at 130°C for 8h. After the reaction was completed, the crude product was dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitated. Centrifugation gave 0.30g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the molecular weight and dispersity of the polymer were determined by GPC. It was determined that the conversion rate of carboxylic acid anhydride was 95%, the number average molecular weight was 4300g / mol, and the molecular weight distribution coefficient was 1.22.

[0131] Example 7

[0132] In a 10mL reaction tube, add trimethylene carbonate (0.490g, 4.80mmol), benzyl alcohol (10μL, 0.096mmol), and the compound of the structure shown in formula I-7 (0.027g, 0.096mmol), and stir magnetically at 90℃ for 4h. After the reaction is completed, the crude product is dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitates. Centrifugal separation obtains 0.32g of a white solid, which is transferred to a vacuum drying oven for drying. The structure of the polymer is identified by NMR, and the following is obtained: Figure 3 shown 1 H NMR spectrum, from Figure 3 It can be seen that the polymer has high purity and low monomer residue. The molecular weight and dispersity of the polymer are determined by GPC. The conversion rate of trimethylene carbonate is 97%, the number average molecular weight is 6300 g / mol, and the molecular weight distribution coefficient is 1.21.

[0133] Example 8

[0134] In a 10mL reaction tube, lactide (0.415g, 2.88mmol), benzyl alcohol (10μL, 0.096mmol), and a compound of the structure shown in formula I-8 (0.026g, 0.096mmol) were added, and magnetic stirring was carried out at 120°C for 4h. After the reaction was completed, the crude product was dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitated. Centrifugation gave 0.30g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the molecular weight and dispersity of the polymer were determined by GPC. It was determined that the conversion rate of lactide was 97%, the number average molecular weight was 4300g / mol, and the molecular weight distribution coefficient was 1.15.

[0135] Example 9

[0136] In a 10mL reaction tube, lactide (0.415g, 2.88mmol), benzyl alcohol (10μL, 0.096mmol), and a compound of the structure shown in formula I-8 (0.038g, 0.096mmol) were added, and magnetic stirring was carried out at 130°C for 4h. After the reaction was completed, the crude product was dissolved in a minimum amount of dichloromethane and then added to a cold methanol solution, and a polymer precipitated. Centrifugation gave 0.29g of a white solid, which was transferred to a vacuum drying oven for drying. The structure of the polymer was identified by NMR, and the molecular weight and dispersity of the polymer were determined by GPC. It was determined that the conversion rate of lactide was 96%, the number average molecular weight was 4300g / mol, and the molecular weight distribution coefficient was 1.20.

[0137] Comparative Example 1

[0138] The method of Preparation Example 1 was followed, except that the compound of formula I-2 was replaced by the compound of formula D-1 obtained in Comparative Preparation Example 1. The conversion rate of lactide was 30%, the number average molecular weight was 1200 g / mol, and the molecular weight distribution coefficient was 1.40.

[0139] Table 1

[0140]

[0141] It can be seen from the results in Table 1 that the monomer conversion rate using the catalyst of the present invention is higher than 90%, which is higher than the monomer conversion rate of Comparative Example 1. Compared with Comparative Example 1, the present application has significantly better effects.

[0142] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A pyridine-acetylsulfonamide compound, characterized in that The pyridine-acetylsulfonamide compound has a structure shown in formula (I): In formula (I), R 1 and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

2. The compound according to claim 1, wherein R 1 is selected from dimethylamino, pyrrolidinyl, tert-butyl or hydrogen; R 2 is selected from hydrogen, methyl, ethyl, butyl, isopropyl or tert-butyl; R 4 is selected from hydrogen or methylphenyl, R 3 is selected from hydrogen, methyl, butyl or phenyl.

3. The compound according to claim 1 or 2, wherein The pyridine-acetylsulfonamide compound has at least one of the structures shown in Formula I-1 to Formula I-9:

4. A method for preparing a pyridine-acetylsulfonamide compound, characterized in that: The preparation method comprises: reacting a pyridine derivative with an acetylsulfonamide compound to obtain a pyridine-acetylsulfonamide compound; wherein the pyridine-acetylsulfonamide compound has a structure shown in formula (I); the pyridine derivative has a structure shown in formula (II); and the acetylsulfonamide compound has a structure shown in formula (III); Among them, R 1 and R 2 Each independently selected from dimethylamino, pyrrolidinyl, hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched alkyl group; R 3 and R 4 Each independently selected from hydrogen, C1-C 10 A substituted or unsubstituted straight chain or branched chain alkyl group.

5. The preparation method according to claim 4, wherein R 1 is selected from dimethylamino, pyrrolidinyl, tert-butyl or hydrogen; R 2 is selected from hydrogen, methyl, ethyl, butyl, isopropyl or tert-butyl; R 4 is selected from hydrogen or methylphenyl, R 3 is selected from hydrogen, methyl, butyl or phenyl; Preferably, the pyridine derivative has at least one of the structures shown in Formula II-1 to Formula II-12: Preferably, the acetylsulfonamide compound has at least one of the structures shown in Formula III-1 to Formula III-6:

6. The preparation method according to claim 4 or 5, wherein: The pyridine-acetylsulfonamide compound has at least one of the structures shown in Formula I-1 to Formula I-9:

7. The preparation method according to any one of claims 4 to 6, wherein: The molar ratio of the pyridine derivative to the acetylsulfonamide compound is 0.5-2:

1.

8. The preparation method according to any one of claims 4 to 7, wherein: The reaction temperature is 25°C-80°C and the reaction time is 6-24h; And / or, the reaction is carried out in a solvent, and the solvent is at least one of tetrahydrofuran, dichloromethane, chloroform and toluene.

9. A pyridine-acetylsulfonamide compound obtained by the preparation method according to any one of claims 4 to 8.

10. The pyridine-acetylsulfonamide compound according to claim 9, wherein The pyridine-acetylsulfonamide compound has at least one of the structures shown in Formula I-1 to Formula I-9:

11. Use of the pyridine-acetylsulfonamide compound according to any one of claims 1 to 3 and 9 to 10 in the preparation of polyester.

12. A method for preparing polyester, characterized in that: The preparation method comprises: in the presence of a catalyst, subjecting a cyclic monomer to a ring-opening polymerization reaction to obtain a polyester; wherein the catalyst is the pyridine-acetylsulfonamide compound according to any one of claims 1-3 and 9-10.

13. The preparation method according to claim 12, wherein: The cyclic monomer is a monomer having a structure represented by formula (IV) or a monomer having a structure represented by formula (V); In formula (IV), A is the general formula [-(CR1R2)-] n The structure shown, n is an integer of 2-10; R1 and R2 are each independently selected from hydrogen, C1-C5 substituted or unsubstituted straight chain or branched alkyl; X is selected from oxygen; In formula (V), A and B are each independently a general formula [-(CR1R2)-] m In the structure shown, m is an integer of 2-10; R1 and R2 are each independently selected from hydrogen, C1-C5 substituted or unsubstituted straight chain or branched alkyl; and X is selected from oxygen.

14. The preparation method according to claim 12 or 13, wherein: The cyclic monomer is β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone or undecalactone; And / or, the cyclic monomer is glycolide, lactide, butyride, decide, decamide, O-carboxylic acid anhydride or N-carboxylic acid anhydride.

15. The preparation method according to any one of claims 12 to 14, wherein: The catalyst is added in an amount of 0.05-10 mol% of the cyclic monomer; And / or, the ring-opening polymerization reaction is carried out at a temperature of 80-140° C. and a time of 0.5-24 h; And / or, the ring-opening polymerization reaction is carried out in the presence of an initiator, and the initiator is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, benzyl alcohol, phenylethyl alcohol, ethylene glycol, 5-hexen-1-ol and water; preferably, the molar ratio of the initiator to the catalyst is 0.01-10:

1.

16. The polyester obtained by the preparation method according to any one of claims 12 to 15, wherein: The polyester has a number average molecular weight of 1000-100000 g / mol, a molecular weight distribution coefficient of 1-2, and a metal content of 0.

17. Use of the polyester according to claim 16 in biomedical materials or food packaging materials.

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