CN113845486B - Anthracene-based macrocyclic molecule, and preparation method and application thereof - Google Patents
Anthracene-based macrocyclic molecule, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of organic synthesis, in particular to an anthracene-based macrocyclic molecule, a preparation method and application thereof. The invention provides an anthracene-based macrocyclic molecule with a structure shown as a formula I, which has a deep cavity structure, and hydrogen bonding sites are arranged in the cavity, so that hydrogen bonds are shielded in the relatively nonpolar deep cavity environment, on one hand, the strength of the hydrogen bonds can be weakened less, and on the other hand, the competition of water molecules to the hydrogen bonding sites is avoided. Therefore, the anthracene-based macrocyclic molecule provided by the invention can simultaneously utilize the hydrophobic effect and hydrogen bond to identify the molecule to be detected, so that the bonding capability of the anthracene-based macrocyclic molecule to the guest molecule is greatly improved. In addition, due to the introduction of the anthracene-based large conjugated system, the macrocyclic molecule has a certain light absorption capacity, and a foundation is laid for detecting and sensing chiral molecules by an optical method. Therefore, the macrocyclic molecule provided by the invention has wide application prospect in the field of molecular recognition.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to an anthracene-based macrocyclic molecule, a preparation method and application thereof.
Background
Molecular recognition is the process by which a host molecule binds to a guest molecule. Molecular recognition, particularly aqueous phase molecular recognition, is very common in biological systems and forms the basis of life phenomena. The research of molecular recognition in the water phase is not only helpful for understanding the recognition process in life activities, but also provides a basis for designing and synthesizing artificial functional molecular recognition systems.
Macrocyclic molecules have wide application in molecular recognition, and traditional macrocyclic host compounds such as cyclodextrin, calixarene, cucurbituril, column arene and the like can be subjected to molecular recognition in a water phase due to the driving of a hydrophobic effect, but the traditional macrocyclic molecules are difficult to meet the recognition and application requirements in a complex environment due to the limited driving force provided by the hydrophobic effect. With the development of organic synthesis technology, new macrocyclic molecules have been developed, but the following problems still remain: (1) The recognition strength for objects in water is generally not high, and particularly it is difficult to recognize electrically neutral hydrophilic molecules, and electrically neutral polar functional groups, with high strength; (2) Groups which generally lack fluorescent properties often can only bind to the guest molecule, but detection of the guest molecule cannot be accomplished optically; (3) Since the nature of intermolecular non-covalent bonds (e.g., hydrogen bonds) is electrostatic, which is inversely proportional to the dielectric constant of the environment in which it is located, a solvent of large dielectric constant (e.g., water) will weaken the strength of weak interactions of intermolecular non-covalent bonds, and thus it is difficult to achieve molecular recognition in solvents of large dielectric constants using actuation of intermolecular non-covalent bonds.
Disclosure of Invention
Based on the above, it is necessary to provide an anthracene-based macrocyclic molecule and a preparation method thereof, wherein the anthracene-based macrocyclic molecule can be used for molecular recognition, especially molecular recognition in water, and has the advantages of being driven by non-covalent bonds, high in recognition strength, capable of realizing detection of guest molecules by an optical method, and the like.
In one aspect of the invention, there is provided an anthracene-based macrocyclic molecule having a structure as shown in formula I:
R 1 ～R 6 are each independently selected from-H, -D or-XR 7 ；
Wherein X is-O-or-CH 2 -；
R 7 Independently selected from the group consisting of linear alkyl, alkoxy, ester, carboxylate substitutions having 1 to 18C atoms for each occurrenceA group, an ammonium salt substituent, a sulfonate substituent, a phosphate substituent, a pyridinium cation substituent, an imidazolium cation substituent, or a branched alkyl or alkoxy group having 3 to 18C atoms.
The anthracene-based macrocyclic molecule provided by the invention has a deep cavity structure, a hydrogen bonding site is arranged in the cavity, and a hydrogen bond is shielded in the relatively nonpolar deep cavity environment, so that on one hand, the strength of the hydrogen bond is less weakened, and on the other hand, the competition of water molecules to the hydrogen bonding site is avoided. Therefore, the anthracene-based macrocyclic molecule provided by the invention can simultaneously utilize hydrophobic effect and hydrogen bond to identify the molecule to be detected, so that the bonding capability of the anthracene-based macrocyclic molecule to the guest molecule is greatly improved, the anthracene-based macrocyclic molecule still can be bonded with the molecule to be detected under the condition of low macrocyclic concentration, and the molecule to be detected can be bonded with the molecule to be detected with high strength under the condition of low concentration. In addition, due to the introduction of the anthracene-based large conjugated system, the macrocyclic molecule has a certain light absorption capacity, and a foundation is laid for detecting and sensing chiral molecules by an optical method. Therefore, the macrocyclic molecule provided by the invention has wide application prospect in the field of molecular recognition.
In some embodiments, the X is-O-.
In some embodiments, the R 7 Each occurrence is independently selected from-H, a linear alkyl group having 1 to 4C atoms, an alkoxy group, an ester group, a carboxylate substituent, or an ammonium salt substituent.
In some embodiments, the R 7 Each occurrence is independently selected from-CH 3 、-CH 2 COOCH 2 CH 3 、-CH 2 COO - NH 4 + or-CH 2 COO - Na + 。
In some embodiments, the R 2 And/or R 5 is-H.
In some embodiments, the R 2 ＝R 5 And said R 1 ＝R 3 ＝R 4 ＝R 6 。
In some embodiments, the anthracenyl macrocyclic molecule is selected from the following compounds:
in another aspect of the present invention, there is also provided a method for preparing the aforementioned anthracenyl macrocyclic molecule, comprising the steps of:
providing rigid bridged dianthracene shown in a formula II-1, and carrying out acylation reaction to prepare dialdehyde rigid bridged dianthracene shown in a formula III-1; preparing a compound shown in a formula IV-1 by amination reaction of dialdehyde rigid bridged dianthracene shown in the formula III-1;
providing rigid bridged dianthracene shown in a formula II-2, and carrying out acylation reaction to prepare dialdehyde rigid bridged dianthracene shown in a formula III-2; preparing a compound shown in a formula IV-2 through oxidation reaction of dialdehyde rigid bridged dianthracene shown in the formula III-2;
cyclizing the compounds shown in IV-1 and IV-2 to prepare the anthracene-based macrocyclic molecule;
wherein R is 1 ～R 6 Is as defined in any of the previous embodiments.
In some embodiments, the acylation reaction of the rigid bridged bisanthracene shown in II-1 and/or II-2 is performed with a molar ratio of rigid bridged bisanthracene shown in II-1 and/or II-2 to the acylating agent of 1: (4-5).
In a further aspect of the invention, the application of the anthracene-based macrocyclic molecules in molecular recognition is also provided.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. Containing a plurality of R as shown in the general formula 1 R is then 1 May be independently selected from different groups.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantane, and the like.
In the present invention, a carboxylate substituent, an ammonium salt substituent, a sulfonate substituent, a phosphate substituent refer to the form of the substituent after salification of the corresponding anion, e.g., a carboxylate substituent refers to a substituent having a salified carboxyl group, e.g., -CH 2 COO - Na + 。
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In one aspect of the invention, there is provided an anthracene-based macrocyclic molecule having a structure as shown in formula I:
R 1 ～R 6 are each independently selected from-H, -D or-XR 7 ；
Wherein X is-O-or-CH 2 -；
R 7 Each occurrence is independently selected from a linear alkyl group having from 1 to 18C atoms, an alkoxy group, an ester group, a carboxylate substituent, an ammonium salt substituent, a sulfonate substituent, a phosphate substituent, a pyridinium cation substituent, an imidazolium cation substituent, or a branched alkyl or alkoxy group having from 3 to 18C atoms.
The anthracene-based macrocyclic molecule provided by the invention has a deep cavity structure, a hydrogen bonding site is arranged in the cavity, and a hydrogen bond is shielded in the relatively nonpolar deep cavity environment, so that on one hand, the strength of the hydrogen bond is less weakened, and on the other hand, the competition of water molecules to the hydrogen bonding site is avoided. Therefore, the anthracene-based macrocyclic molecule provided by the invention can simultaneously utilize hydrophobic effect and hydrogen bond to identify the molecule to be detected, so that the bonding capability of the anthracene-based macrocyclic molecule to the guest molecule is greatly improved, the anthracene-based macrocyclic molecule still can be bonded with the molecule to be detected under the condition of low macrocyclic concentration, and the molecule to be detected can be bonded with the molecule to be detected with high strength under the condition of low concentration. In addition, due to the introduction of the anthracene-based large conjugated system, the macrocyclic molecule has a certain light absorption capacity, and a foundation is laid for detecting and sensing chiral molecules by an optical method. Therefore, the macrocyclic molecule provided by the invention has wide application prospect in the field of molecular recognition.
In some embodiments, X is-O-. When X is oxygen, more tail chains are connected to the anthracenyl macrocyclic molecules, so that the hydrophobic property of the anthracenyl macrocyclic molecules can be regulated and controlled by adjusting the types or lengths of the tail chains, the binding of different guest molecules can be dealt with, the sensitivity of molecular recognition is greatly improved, the possibility of molecular recognition under the conditions of low concentration of the guest molecules or low concentration of the macrocyclic molecules is realized, and the application scene of molecular recognition is effectively expanded.
In some embodiments, R 7 Each occurrence is independently selected from-H, a linear alkyl group having 1 to 4C atoms, an alkoxy group, an ester group, a carboxylate substituent, or an ammonium salt substituent.
In some embodiments, R 7 Each occurrence is independently selected from-CH 3 、-CH 2 COOCH 2 CH 3 、-CH 2 COO - NH 4 + or-CH 2 COO - Na + 。
In some embodiments, R 2 And/or R 5 is-H.
In some embodiments, preferably, R 2 ＝R 5 And R is 1 ＝R 3 ＝R 4 ＝R 6 。
In some embodiments, the anthracene-based macrocyclic molecule is selected from the following compounds:
in another aspect of the present invention, there is also provided a method for preparing the aforementioned anthracenyl macrocyclic molecule, comprising the steps of:
providing rigid bridged dianthracene shown in a formula II-1, and carrying out acylation reaction to prepare dialdehyde rigid bridged dianthracene shown in a formula III-1; preparing a compound shown in a formula IV-1 by amination reaction of dialdehyde rigid bridged dianthracene shown in the formula III-1;
providing rigid bridged dianthracene shown in a formula II-2, and carrying out acylation reaction to prepare dialdehyde rigid bridged dianthracene shown in a formula III-2; preparing a compound shown in a formula IV-2 through oxidation reaction of dialdehyde rigid bridged dianthracene shown in the formula III-2;
cyclizing the compounds shown in IV-1 and IV-2 to prepare anthryl macrocyclic molecules;
wherein R is 1 ～R 6 Is as defined in any of the previous embodiments.
In some embodiments, the acylation reaction of the rigid bridged bisanthracene shown in II-1 and/or II-2 is performed with a molar ratio of rigid bridged bisanthracene shown in II-1 and/or II-2 to the acylating agent of 1: (4-5).
In some embodiments, the acylating reagent of the acylation reaction of rigid bridged dianthracenes as shown in II-1 and/or II-2 is 1, 1-dichloromethyl ether, the catalyst is titanium tetrachloride, and the solvent is methylene chloride; the molar ratio of the rigid bridged bisanthracene shown in II-1 and/or II-2 to the acylating agent and the catalyst is 1: (4-5): (4-5). Alternatively, the molar ratio of rigid bridged bisanthracene to acylating agent and catalyst as shown in II-1 and/or II-2 may be, for example, 1: (4.2-4.8): (4.2-4.8), and can also be 1: (4.4 to 4.6): (4.4-4.6).
In some embodiments, the acylation reaction comprises the steps of:
dissolving the rigid bridged dianthracene shown in II-1 and/or II-2 in dichloromethane, adding 1, 1-dichloro methyl ether, cooling to 0+/-2 ℃, and dripping titanium tetrachloride under stirring. Continuously maintaining the temperature of the system at 0+/-2 ℃ for 0.8-1.2 hours, preferably 1 hour after dripping, and then heating to room temperature and maintaining for 2-4 hours, preferably 3 hours; pouring the reaction liquid into ice water, and regulating the pH value to be 6-8. Then extracting, merging organic phases, removing the organic solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain the dialdehyde group rigid bridged dianthracene.
In some embodiments, the cyclization reaction comprises the steps of:
oxidation product IV-2 and benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate (PyBOP) were dissolved in dry N, N-Dimethylformamide (DMF), and amination product IV-1 was dissolved in another portion of dry DMF. The two solutions are simultaneously added dropwise to dry DMF in which N, N-Diisopropylethylamine (DIPEA) is dissolved under nitrogen protection for 5 to 7 hours, preferably 6 hours. Then stirring for 22-26 h, preferably 24h at room temperature under the protection of nitrogen. Then, spin-drying most of the solvent under reduced pressure, and pouring the rest solution into ice water to separate out precipitate; and separating and purifying the precipitate by column chromatography to obtain the solid product of the anthracene-based macrocyclic molecule I.
In some embodiments, the molar ratio of amination product IV-1, oxidation product IV-2, pyBOP, and DIPEA is 1:1: (2.5-3.5): (29-31), preferably, the molar ratio is 1:1:3:30.
In some embodiments, the amination reaction comprises the steps of:
rigid bridging of dialdehyde groups with dianthracenes, triethylsilane, tert-butyl carbamate (BocNH) 2 ) And trifluoroacetic acid in a mixed solution of acetonitrile and dichloromethane. Stirring for 11-13 h, preferably 12h at room temperature under the protection of nitrogen. The solvent is dried by spin drying under reduced pressure, dichloromethane and trifluoroacetic acid are added, and stirring is carried out for 11h to 12h, preferably 12h under the protection of nitrogen. Most of the organic solvent is removed by spin-drying under reduced pressure, diethyl ether is added, and precipitation is separated out. The precipitate was filtered to give the amination product.
In some embodiments, the molar ratio of dialdehyde group rigid bridged dianthracene, triethylsilane, t-butyl carbamate, trifluoroacetic acid is 1: (6.5-7.5): (6.5-7.5): (3-5), preferably, the molar ratio is 1:7:7:4.
In some embodiments, the oxidation reaction comprises the steps of:
rigid bridging of dialdehyde groups with dianthracenes and NH 2 SO 3 H and NaClO 2 Dissolved in H 2 O, meOH and THF, stirring at room temperature for 11-12 hr, preferably 12 hr, pouring into water to separate out precipitate, and filtering to obtain oxidized product.
In some embodiments, the dialdehyde group is a rigid bridged bis anthracene, NH 2 SO 3 H and NaClO 2 The molar ratio of (2) is 1: (7.5-8.5): (7.5 to 8.5), preferably in a molar ratio of 1:8:8.
In some embodiments, H 2 O, meOH and THF in a volume ratio of 1: (0.8-1.2): (0.8-1.2), preferably, the volume ratio is 1:1:1.
In some embodiments, the rigid bridged bisanthracene may be prepared by the following method:
in a further aspect of the invention, the application of the anthracene-based macrocyclic molecules in molecular recognition is also provided.
Preferably, the anthracenyl macrocyclic molecules of the present invention are particularly useful for the recognition of quinone-based compounds and compounds containing a 1, 4-dioxane backbone.
The invention also provides application of the anthracenyl macrocyclic molecule in chiral molecule detection and sensing. According to the invention, due to the introduction of the anthracene group, the macrocyclic molecular host has a certain light absorption property, so that the bonded guest molecules can be detected through the circular dichroism spectrum even if no circular dichroism spectrum signal exists, and therefore, the detection and the sensing of the chiral molecules are realized, and the method has a wide application prospect.
The present invention will be described in further detail with reference to specific examples and comparative examples. It is understood that the instruments and materials used in the following examples are more specific and in other embodiments may not be so limited.
Example 1
(1) Preparation of the dialdehyde rigid bridged dianthracene compound a:
intermediate compound S 0 Is prepared from the following steps: 9-Bromoanthracene (12 g,45 mmol) was dissolved in dry tetrahydrofuran (300 mL) and a dry tetrahydrofuran solution of n-butyllithium (2.60M, 19.2mL,50.6 mmol) was added under nitrogen at low temperature-80 ℃. After maintaining at-80℃and stirring for two hours, zinc chloride (9.1 g,66.7 mmol) was added. Maintaining the temperature at-80 ℃, stirring for four hours, then heating to room temperature, and stirring for one day. 1, 3-dibromo-4, 6-dimethoxybenzene (3.4 g,11.5 mmol), bis (cyanobenzene) palladium dichloride (0.44 g,1.2 mmol) and a solution of tri-tert-butylphosphine in n-hexane (10% wt,5.6mL,2.3 mmol) were added to 50mL dry tetrahydrofuran and stirred at room temperature under nitrogen for half an hour. The solution was transferred and injected into a reaction system which had been stirred at room temperature for one day before, and then heated to 85℃and stirred for two days. And then cooling the reaction to room temperature, and filtering the solution to obtain a filter cake, namely a crude product. Sequentially washing with methanol, n-hexane and chloroform to obtain yellow solid product S 0 (5.0g,yield 94％)。
Preparation of Compound A: intermediate S 0 (4.9 g,10.0mmol,1 equiv.) is dissolved in 200mL dichloromethane, 1-dichloromethyl ether (3.6 mL,40.0mmol,4 equiv.) is added, cooled to 0deg.C, and TiCl is added dropwise with stirring 4 (4.0 mL,40.0mmol,4 equiv.). After the completion of the dripping, the temperature was maintained at 0℃for one hour, and then the mixture was warmed to room temperature and maintained for three hours. The reaction mixture was poured into ice water (200 mL), the pH was adjusted to 6 to 8 with an aqueous sodium hydroxide solution, and extraction was performed with methylene chloride (200 mL. Times.3). The organic phases were combined and the organic solvent was removed by rotary evaporation under reduced pressure. The resulting solid was isolated and purified by column chromatography to give compound a (4.9 g, yield90%) as a yellow solid.
And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization on the obtained product compound A, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝11.54(s,2H),8.98(d,J＝8.8Hz,4H),8.00(d,J＝8.8Hz,4H),7.68(dd,J＝8.8,6.6Hz,4H),7.54(dd,J＝8.8,6.6Hz,4H),7.11(s,1H),7.03(s,1H),3.81(s,6H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝193.32,159.04,141.86,135.00,131.58,130.45,128.50,127.72,125.63,125.20,123.61,118.56,95.97,55.99.ESI-TOF-HRMS:m/z calcd for[M+H] + C 38 H 27 O 4 + ,547.1904；found 547.1910(error＝+1.1ppm).
(2) Anthracenyl macrocyclic molecules M 1 Is prepared from the following steps:
intermediate compound S 3 Is prepared by synthesizing NaClO 2 (1.8 g,20.0 mmol), compound A (1.3 g,2.5 mmol) and NH 2 SO 3 H (1.9 g,20.0 mmol) was dissolved in H 2 O (10 mL), THF (10 mL) and MeOH (10 mL). Stirred at room temperature for 12 hours, poured into 300mL of water to precipitate. Filtering to obtain a product S 3 (1.1g,yield 77％)。
Intermediate compound S 4 Triethylsilane (2.8 mL,17.5 mmol), compound A (1.3 g,2.5 mmol), tert-butyl carbamate (2.0 g,17.5 mmol) and trifluoroacetic acid (0.7 mL,10 mmol) were dissolved in a mixed solution of acetonitrile (20 mL) and dichloromethane (20 mL). Stirring at room temperature for 12 hours under nitrogen protection. The solvent was dried under reduced pressure, dichloromethane (20 mL) and trifluoroacetic acid (20 mL) were added and stirred under nitrogen for 12 hours. Most of the organic solvent was removed by spinning under reduced pressure, diethyl ether (50 mL) was added to precipitate. Filtering the precipitate to obtain a solid product compound S 4 (1.8g,yield 95％)。
Macrocyclic molecules M 1 Is prepared from the intermediate compound S 3 (578 mg,1 mmol) and benzotriazol-1-yl-oxy-tripyrrole hexafluorophosphateAlkyl phosphorus (PyBOP, 1.6g,3 mmol) was dissolved in dry N, N-dimethylformamide (30 mL.) Compound S 4 (749 mg,1 mmol) was dissolved in another portion of dry DMF (30 mL). The two solutions were added dropwise to dry N, N-dimethylformamide (400 mL) dissolved in N, N-diisopropylethylamine (3.9 g,5.0 mL) under nitrogen atmosphere, and the mixture was left to drop over 6 hours. Stirring at room temperature for 24 hours under nitrogen protection. Most of the solvent was dried by spin-drying under reduced pressure, and the remaining solution was poured into ice water to precipitate out. Separating and purifying by column chromatography to obtain solid product macrocyclic molecule M 1 (490mg,yield 45％)。
For the obtained product macrocyclic molecule M 1 And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝8.39(d,J＝8.8Hz,4H),8.13(d,J＝8.8Hz,4H),7.68(d,J＝8.8Hz,4H),7.60(d,J＝8.8Hz,4H),7.53(dd,J＝8.8,6.6,4H),7.35(m,8H),7.25(dd,J＝8.8,6.6,4H),7.00(s,1H),6.99(s,1H),6.03(s,1H),5.85(s,1H),5.78(d,J＝4.1Hz,4H),5.04(t,J＝4.2Hz,2H),3.90(s,6H),3.88(s,6H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝168.63,158.54,158.48,138.03,136.95,135.46,135.11,131.88,130.54,129.90,129.44,128.21,127.57,127.47,126.89,126.23,126.01,125.16,125.10,124.94,123.68,119.07,118.79,95.72,95.50,56.02,55.96,36.46.ESI-TOF-HRMS:m/z calcd for[M+N(CH 3 ) 4 ] + C 80 H 66 N 3 O 6 + ,1164.4946；found 1164.4969(error＝+2.0ppm).
example 2
(1) Preparation of the dialdehyde rigid bridged dianthracene compound B:
synthesis of intermediate S 1 Compounds S 0 (2.4 g,5.0 mmol) was dissolved in 50mL of dichloromethane and BBr was added at 0deg.C 3 (5.0 mL,50.0 mmol). After stirring at 0℃for half an hour, the mixture was warmed to room temperature and stirred for four hours. Will beThe reaction solution was poured into an ice-water bath, and the pH was adjusted to 5-6 with NaOH solution, and extracted with methylene chloride (50 mL. Times.3) and ethyl acetate (50 mL. Times.3). Combining the organic phases, and removing the organic solvent under reduced pressure to obtain a solid product S 1 (2.9g,90％).
Preparation of Compound B intermediate S 1 (6.3 g,10.0 mmol) was dissolved in 200mL of methylene chloride, 1-dichloromethyl ether (3.6 mL,40.0 mmol) was added, the temperature was lowered to 0℃and TiCl was added dropwise with stirring 4 (4.0 mL,40.0 mmol). After the completion of the dripping, the temperature was maintained at 0℃for one hour, and then the mixture was warmed to room temperature and maintained for three hours. The reaction mixture was poured into ice water (200 mL), the pH was adjusted to 6 to 8 with an aqueous sodium hydroxide solution, and extraction was performed with methylene chloride (200 mL. Times.3). The organic phases were combined and the organic solvent was removed by rotary evaporation under reduced pressure. The resulting solid was isolated and purified by column chromatography to give compound B (5.9 g, yield 85%) as a yellow solid.
And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization on the obtained product compound B, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝11.54(s,2H),8.97(d,J＝9.0Hz,4H),8.02(d,J＝8.7Hz,4H),7.68(dd,J＝9.0,6.6Hz,4H),7.56(dd,J＝8.7,6.6Hz,2H),7.18(s,1H),6.74(s,1H),4.55(s,4H),4.16(q,J＝7.1Hz,4H),1.22(t,J＝7.1Hz,6H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝193.34,168.16,157.10,140.86,135.75,131.48,130.37,128.52,127.72,125.72,125.48,123.60,120.23,98.07,65.86,61.41,13.87.ESI-TOF-HRMS:m/z calcd for[M+H] + C 44 H 35 O 8 + ,691.2326；found 691.2335(error＝+1.3ppm).
(2) Anthracenyl macrocyclic molecules M 2 Is prepared from the following steps:
intermediate compound S 5 Is prepared by synthesizing NaClO 2 (1.1 g,12.0 mmol), compound B (1.0 g,1.5 mmol) and NH 2 SO 3 H (1.2 g,12.0 mmol) was dissolved in H 2 O (8 mL), THF (8 mL) and MeOH (8 mL) in a mixtureMixing the above solutions. Stirred at room temperature for 12 hours, poured into 300mL of water to precipitate. Filtering to obtain a product S 5 (0.9g,yield 87％)。
Intermediate compound S 6 Triethylsilane (1.7 mL,10.5 mmol), compound B (1.0 g,1.5 mmol), tert-butyl carbamate (1.2 g,10.5 mmol) and trifluoroacetic acid (0.4 mL,6 mmol) were dissolved in a mixed solution of acetonitrile (15 mL) and dichloromethane (15 mL). Stirring at room temperature for 12 hours under nitrogen protection. The solvent was dried under reduced pressure, dichloromethane (15 mL) and trifluoroacetic acid (15 mL) were added and stirred under nitrogen for 12 hours. Most of the organic solvent was removed by spinning under reduced pressure, diethyl ether (50 mL) was added to precipitate. Filtering the precipitate to obtain a solid product compound S 6 (1.1g,yield 83％)。
Macrocyclic molecules M 2 Is prepared from the intermediate compound S 5 (723 mg,1 mmol) and benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate (PyBOP, 1.6g,3 mmol) in dry N, N-dimethylformamide (30 mL) Compound S was dissolved 6 (921 mg,1 mmol) was dissolved in another portion of dry DMF (30 mL). The two solutions were simultaneously added dropwise to dry N, N-dimethylformamide (400 mL) dissolved in N, N-diisopropylethylamine (3.9 g,5.0 mL) under nitrogen protection, and the mixture was added dropwise over 6 hours. Stirring at room temperature for 24 hours under nitrogen protection. Most of the solvent was dried by spin-drying under reduced pressure, and the remaining solution was poured into ice water to precipitate out. Separating and purifying by column chromatography to obtain solid product macrocyclic molecule M 2 (730mg,yield 53％)。
For the obtained product macrocyclic molecule M 2 And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝8.40(d,J＝8.7Hz,4H),8.13(d,J＝8.7Hz,4H),7.72(d,J＝8.7Hz,4H),7.65(d,J＝8.7Hz,4H),7.59–7.50(m,4H),7.42–7.33(m,8H),7.31–7.24(m,4H),6.74(s,1H),6.73(s,1H),6.10(s,1H),5.92(s,1H),5.79(d,J＝4.2Hz,4H),5.09(t,J＝4.2Hz,2H),4.20(q,J＝7.1Hz,8H),1.25(t,J＝7.1Hz,12H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝168.66,168.42,168.41,156.61,156.55,138.82,137.76,134.62,134.28,132.11,130.48,129.85,129.43,128.48,127.58,127.46,126.90,126.31,126.12,125.30,125.14,125.10,123.68,120.75,120.50,98.45,97.82,65.97,65.84,61.36,36.49,31.58,22.65,13.86.ESI-TOF-HRMS:m/z calcd for[M+K] + Chemical Formula:C 88 H 70 KN 2 O 14 + ,1417.4459；found 1417.4485(error＝+1.8ppm).
example 3
Anthracenyl macrocyclic molecules M 3 Is prepared from the following steps:
the anthracenyl macrocyclic molecule M prepared in example 2 2 (690 mg,0.5 mmol) in a mixture of ethanol (10 mL) and water (10 mL) was added sodium hydroxide (800 mg). After stirring at room temperature for 12 hours, the solvent was dried under reduced pressure. To the residue was added dropwise 10% hcl solution (5 mL) to give a large amount of solid precipitate. The resulting solid was filtered and lyophilized under reduced pressure to give a solid (500 mg). The above solid was added to water (5 mL) in which sodium hydroxide (64 mg) was dissolved, and stirred for two hours. Freeze drying the solution to obtain solid product macrocyclic molecule M 3 (540mg,yield 80％)。
For the obtained product macrocyclic molecule M 3 And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization, wherein the data result is as follows:
1 H NMR(500MHz,D 2 O,298K)δ[ppm]＝8.34(d,J＝8.8Hz,4H),7.91(d,J＝8.8Hz,4H),7.73(d,J＝8.8Hz,4H),7.65(d,J＝8.8Hz,4H),7.50(dd,J＝8.8,8.3Hz,4H),7.33(m,8H),7.23(dd,J＝8.8,8.3Hz,4H),6.73(s,1H),6.69(s,1H),5.83(s,1H),5.71(s,4H),5.67(s,1H),4.38(s,4H),4.36(s,4H). 13 C NMR(126MHz,D 2 O/DMSO-d 6 ＝9:1,298K)δ[ppm]＝175.85,171.20,163.81,157.16,157.02,138.18,136.85,135.55,134.65,130.38,130.23,129.61,129.50,127.75,127.52,127.19,127.09,126.90,126.67,125.95,125.67,124.51,123.84,119.87,119.27,98.55,98.26,67.70,67.61,36.36.ESI-TOF-HRMS:m/z calcd for[M-4Na + ] 3- C 80 H 51 N 2 O 14 3- ,421.1119；found 421.1112(error＝-1.7ppm).
example 4
(1) Preparation of dialdehyde rigid bridged dianthracene compound C:
intermediate compound S 7 Is prepared from the following steps: 9-Bromoanthracene (12 g,45 mmol) was dissolved in dry tetrahydrofuran (300 mL) and a dry tetrahydrofuran solution of n-butyllithium (2.60M, 19.2mL,50.6 mmol) was added under nitrogen at low temperature-80 ℃. After maintaining at-80℃and stirring for two hours, zinc chloride (9.1 g,66.7 mmol) was added. Maintaining the temperature at-80 ℃, stirring for four hours, then heating to room temperature, and stirring for one day. 1, 3-dibromo-4, 5, 6-trimethoxybenzene (3.7 g,11.5 mmol), bis (cyanobenzene) palladium dichloride (0.44 g,1.2 mmol) and tri-tert-butylphosphine in n-hexane (10% wt,5.6mL,2.3 mmol) were added to 50mL dry tetrahydrofuran and stirred at room temperature under nitrogen for half an hour. The solution was transferred and injected into a reaction system which had been stirred at room temperature for one day before, and then heated to 85℃and stirred for two days. And then cooling the reaction to room temperature, and filtering the solution to obtain a filter cake, namely a crude product. Sequentially washing with methanol, n-hexane and chloroform to obtain yellow solid product S 7 (5.3g,yield 94％)。
Preparation of compound C: intermediate S 7 (5.2 g,10.0mmol,1 equiv.) is dissolved in 200mL dichloromethane, 1-dichloromethyl ether (3.6 mL,40.0mmol,4 equiv.) is added, cooled to 0deg.C, and TiCl is added dropwise with stirring 4 (4.0 mL,40.0mmol,4 equiv.). After the completion of the dripping, the temperature was maintained at 0℃for one hour, and then the mixture was warmed to room temperature and maintained for three hours. The reaction mixture was poured into ice water (200 mL), the pH was adjusted to 6 to 8 with an aqueous sodium hydroxide solution, and extraction was performed with methylene chloride (200 mL. Times.3). The organic phases were combined and the organic solvent was removed by rotary evaporation under reduced pressure. The resulting solid was isolated and purified by column chromatography to give compound C (5.4 g, yield94%) as a yellow solid.
And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization on the obtained product compound C, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝11.32(s,2H),8.98(d,J＝8.8Hz,4H),7.87(d,J＝8.8Hz,4H),7.46(dd,J＝8.8,6.6Hz,4H),7.33(dd,J＝8.8,6.6Hz,4H),6.98(s,1H),3.74(s,6H),3.61(s,3H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝188.67,156.34,138.75,131.83,129.41,127.31,124.34,119.68,116.56,114.34,111.58,109.87,94.77,53.72,51.98.ESI-TOF-HRMS:m/z calcd for[M+H] + C 39 H 30 O 5 + ,577.2010；found 577.2018(error＝+1.4ppm).
(2) Anthracenyl macrocyclic molecules M 4 Is prepared from the following steps:
intermediate compound S 8 Is prepared by synthesizing NaClO 2 (1.8 g,20.0 mmol), compound C (1.4 g,2.5 mmol) and NH 2 SO 3 H (1.9 g,20.0 mmol) was dissolved in H 2 O (10 mL), THF (10 mL) and MeOH (10 mL). Stirred at room temperature for 12 hours, poured into 300mL of water to precipitate. Filtering to obtain a product S 8 (1.3g,yield 83％)。
Intermediate compound S 9 Triethylsilane (2.8 mL,17.5 mmol), compound A (1.4 g,2.5 mmol), tert-butyl carbamate (2.0 g,17.5 mmol) and trifluoroacetic acid (0.7 mL,10 mmol) were dissolved in a mixed solution of acetonitrile (20 mL) and dichloromethane (20 mL). Stirring at room temperature for 12 hours under nitrogen protection. The solvent was dried under reduced pressure, dichloromethane (20 mL) and trifluoroacetic acid (20 mL) were added and stirred under nitrogen for 12 hours. Most of the organic solvent was removed by spinning under reduced pressure, diethyl ether (50 mL) was added to precipitate. Filtering the precipitate to obtain a solid product compound S 9 (1.8g,yield 87％)。
Macrocyclic molecules M 1 Is prepared from the intermediate compound S 8 (608 mg,1 mmol) and benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate (PyBOP, 1.6g,3 mmol) were dissolved in dry N, N-dimethylformamide (30 mL) 9 (806 mg,1 mmol) in another portion of dryDry DMF (30 mL). The two solutions were simultaneously added dropwise to dry N, N-dimethylformamide (400 mL) dissolved in N, N-diisopropylethylamine (3.9 g,5.0 mL) under nitrogen protection, and the mixture was added dropwise over 6 hours. Stirring at room temperature for 24 hours under nitrogen protection. Most of the solvent was dried by spin-drying under reduced pressure, and the remaining solution was poured into ice water to precipitate out. Separating and purifying by column chromatography to obtain solid product macrocyclic molecule M 4 (610mg,yield 53％)。
For the obtained product macrocyclic molecule M 4 And (3) performing nuclear magnetic hydrogen spectrum, nuclear magnetic carbon spectrum and mass spectrum characterization, wherein the data result is as follows:
1 H NMR(500MHz,CD 2 Cl 2 ,298K)δ[ppm]＝8.28(d,J＝8.8Hz,4H),8.01(d,J＝8.8Hz,4H),7.52(d,J＝8.8Hz,4H),7.50(d,J＝8.8Hz,4H),7.38(dd,J＝8.8,6.6,4H),7.24(m,8H),7.12(dd,J＝8.8,6.6,4H),5.97(s,1H),5.71(s,1H),5.65(d,J＝4.1Hz,4H),4.90(t,J＝4.2Hz,2H),3.80(s,6H),3.76(s,6H),3.70(s,3H),3.64(s,3H). 13 C NMR(126MHz,CD 2 Cl 2 ,298K)δ[ppm]＝161.32,152.38,150.54,131.98,128.33,127.68,125.34,123.47,120.34,119.53,117.49,115.98,113.75,112.63,111.04,110.84,110.56,108.93,108.67,107.94,107.63,106.70,106.21,93.59,92.14,53.83,52.77,33.44,29.36.ESI-TOF-HRMS:m/z calcd for[M+N(CH 3 ) 4 ] + C 82 H 70 N 3 O 8 + ,1224.5157；found 1224.5178(error＝+1.7ppm).
performance test:
(1) Molecular recognition
a. Macrocyclic molecule M prepared in example 1 1 For organic micromolecular benzoquinone (G) in organic solvent 1 ) Naphthoquinone (G) 2 ) And anthraquinone (G) 3 ) Molecular recognition of (a). Determination of the binding constant (K) of macrocyclic molecules to guest molecules of different Structure in dichloromethane by means of Nuclear magnetic titration a ) The test data are shown in table 1.
The model of the nuclear magnetic instrument is Bruker Avance-500 NMR spectrometer solvent which is deuterated dichloromethane; the temperature is 25 ℃; the concentration of the main body is 0.3mM; guest concentration 8mM.
TABLE 1
| Object | G 1 | G 2 | G 3 |
| Bonding constant (K) a /M -1 ) | 4 | 11 | 94 |
As can be seen from the data in Table 1, the macrocyclic compound M1 recognizes important small organic molecules of biological and medicinal significance in organic solvents, such as quinone compounds benzoquinone (G1), naphthoquinone (G2) and anthraquinone (G3). And, the recognition of these compounds has a remarkable selectivity, for example, the binding constant to anthraquinone (G3) is 23 times that of benzoquinone (G1).
b. Macrocyclic molecule M prepared in example 3 3 Is used for preparing organic micromolecular benzoquinone (G) 1 ) Vitamin K 3 (G 4 ) 1, 4-Dioxahexacyclic ring (G) 5 ) Chromone (G) 6 ) Molecular recognition of (a). Determination of the binding constant (K) of macrocyclic molecules to the above-mentioned guest molecules of different structures in water by isothermal titration calorimetry a ) The test data are shown in table 2.
The model number of the isothermal titration calorimeter is Malvern MicroCal PEAQ-ITC Automated instrument; solvent, ultrapure water; the temperature is 25 ℃; the concentration of the main body is 0.1mM; guest concentration 1.1mM.
TABLE 2
| Object | G 1 | G 4 | G 5 | G 6 |
| Bonding constant (K) a /M -1 ) | 3.0×10 4 | 5.7×10 6 | 1.1×10 3 | 4.1×10 5 |
As can be seen from the data in Table 2, macrocyclic molecule M 3 Organic small molecules with biological and medical significance, such as quinone compounds benzoquinone (G) 1 ) Vitamin K 3 (G 4 ) Chromone of drug mother nucleus structure (G) 6 ). And, the recognition of these compounds is clearly selective. For the water-miscible environmental pollutants 1, 4-dioxane (G) 5 ) Is bonded to 10 3 M -1 The above indicates that macrocyclic molecule M 3 Hydrophilic molecules can be well recognized in water.
(2) Chiral sensing:
macrocyclic molecule M prepared in example 3 3 The method is used for chiral sensing of chiral small organic molecules in an aqueous phase. Macrocyclic molecules M 3 Is an achiral molecule, the solution of which does not have a circular dichroism spectrum signal. Levetiracetam (Levetiracetam), the aliases Levetiracetam, lividracetam, levetiracetam, chemical name (S) -alpha-ethyl-2-oxo-1-pyrrolidineacetamide, a chemical of white crystalline powder; the compound is chiral, but does not have a circular dichroism spectrum signal. When one stoichiometric amount (50. Mu.M) of levetiracetam was added to the aqueous solution of macrocyclic molecules 3-4 (50. Mu.M), the complex solution showed a pronounced circular dichroism spectrum signal at wavelengths of 250-290 nm, 310-420 nm. This indicates that macrocyclic molecules 3-4 can be used to detect and sense chiral signals of chiral molecules.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (11)
1. An anthracenyl macrocyclic molecule having a structure according to formula I:
；
R 1 、R 3 、R 4 and R is 6 Are each independently selected from-XR 7 ；
R 2 And R is 5 Are each independently selected from-H, -D or-XR 7 ；
Wherein X is-O-or-CH 2 -；
R 7 Each occurrence is independently selected from a linear alkyl group having 1 to 4C atoms, an ester group having 1 to 4C atoms, a carboxylate substituent having 1 to 4C atoms, or an ammonium salt substituent having 1 to 4C atoms;
the carboxylate substituents and ammonium salt substituents refer to the salt-forming forms of the corresponding anions in the substituents.
2. The anthracenyl macrocyclic molecule of claim 1, wherein X is-O-.
3. The anthracenyl macrocyclic molecule of claim 1, wherein R 7 Each occurrence is independently selected from-CH 3 、-CH 2 COOCH 2 CH 3 、-CH 2 COO - NH 4 + or-CH 2 COO - Na + 。
4. The anthracenyl macrocyclic molecule of claim 1, wherein R 2 Or R is 5 is-H.
5. The anthracenyl macrocyclic molecule of claim 1, wherein R 2 And R is 5 is-H.
6. The anthracene-based macrocyclic molecule of any one of claims 1-5, wherein R 2 =R 5 And said R 1 =R 3 =R 4 =R 6 。
7. The anthracenyl macrocyclic molecule of claim 1, wherein the anthracenyl macrocyclic molecule is selected from the group consisting of:
。
8. the method for preparing the anthracene-based macrocyclic molecule of any one of claims 1 to 7, characterized by comprising the following steps:
providing rigid bridged dianthracene shown in a formula II-1, and carrying out acylation reaction to prepare dialdehyde rigid bridged dianthracene shown in a formula III-1; preparing a compound shown in a formula IV-1 by amination reaction of dialdehyde rigid bridged dianthracene shown in the formula III-1;
providing rigid bridged dianthracene shown in a formula II-2, carrying out acylation reaction on the rigid bridged dianthracene to prepare dialdehyde rigid bridged dianthracene shown in a formula III-2, and carrying out oxidation reaction on the dialdehyde rigid bridged dianthracene shown in the formula III-2 to prepare a compound shown in a formula IV-2;
；
cyclizing the compounds shown in IV-1 and IV-2 to prepare the anthracene-based macrocyclic molecule;
wherein R is 1 ~R 6 Is as defined in any one of claims 1 to 7.
9. The process according to claim 8, wherein in the acylation reaction of the rigid bridged dianthracene represented by II-1 and II-2, the molar ratio of the rigid bridged dianthracene represented by II-1 and II-2 to the acylating agent is 1: (4-5).
10. The preparation method according to claim 8, wherein the acylating reagent for the acylation reaction of the rigid bridged dianthracene shown in II-1 and II-2 is 1, 1-dichloromethyl ether, the catalyst is titanium tetrachloride, and the solvent is dichloromethane; the molar ratio of the rigid bridged bisanthracene to the acylating agent and the catalyst shown in II-1 and II-2 is 1: (4-5): (4-5).
11. Use of the anthracene-based macrocyclic molecule of any one of claims 1-7 in molecular recognition.
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