Preparation method of rotaxane mechanical interlocking molecule

Abstract

The invention provides a preparation method of rotaxane mechanical interlocking molecules. According to the preparation method, under the condition of not adding a catalyst, dibenzene-24-crown-8, benzene-21-crown-7, an isocyanate derivative and a rod-shaped compound are subjected to a reaction by adopting a one-pot method to obtain the rotaxane mechanical interlocking molecule. The preparation method not only can reach 100% of atom economy and meet the requirements of green chemistry, but also can reach the yield of 65% or above, and realizes efficient preparation of rotaxane mechanical interlocking molecules.

Description

Technical Field

[0001] The present invention belongs to the technical field of mechanical interlocking molecules, and more specifically, relates to a method for preparing rotaxane mechanical interlocking molecules. Background Art

[0002] Mechanically interlocked molecules (MIMs) refer to structures in which at least two components in a molecule are intertwined and interlocked through mechanical bonds. Their characteristics are that there are no direct covalent bonds between the components, but these components cannot be separated without cutting the covalent bonds, thus ensuring that the mechanically interlocked molecules have a high degree of conformational freedom (such as elongation, rotation, sliding and twisting, etc.) while maintaining structural integrity.

[0003] Mechanically interlocked molecules can be divided into rotaxanes, molecular knots, catenanes, etc. according to their structures. Rotaxane mechanically interlocked molecules have rod-shaped molecules as the axis component and ring-shaped molecules as the ring component. The rod-shaped molecules pass through the cavity of the ring-shaped molecules, and large molecules are bound at both ends to prevent the rod-shaped molecules from slipping out. Therefore, rotaxane mechanically interlocked molecules have high degrees of freedom, mobility and structural stability, and are widely used in molecular machines, reaction intermediates, catalysts, drug delivery systems, etc.

[0004] At present, the preparation process of rotaxane mechanical interlocking molecules often requires the use of heavy metals (such as tin ions, etc.) as catalysts, but heavy metals are prone to cause environmental pollution. Therefore, it is urgent to find a green method for preparing rotaxane mechanical interlocking molecules. Summary of the invention

[0005] The present invention aims to provide a method for preparing rotaxane mechanical interlocking molecules in view of the deficiencies of the prior art, wherein dibenzo-24-crown-8 and benzo-21-crown-7 are used as the ring components of the rotaxane mechanical interlocking molecules, a rod-shaped compound is used as the axis component, an isocyanate derivative is used as the blocking group, and the hydroxyl group of the rod-shaped compound is used as the reactive group, and the rotaxane mechanical interlocking molecules are prepared by a one-pot method without adding a catalyst. The method can not only achieve 100% atom economy, meet the requirements of green chemistry, but also achieve a yield of more than 65%, realizing the efficient preparation of rotaxane mechanical interlocking molecules.

[0006] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0007] The present invention provides a method for preparing a rotaxane mechanical interlocking molecule, which is obtained by reacting dibenzo-24-crown-8 (DB24C8), benzo-21-crown-7 (B21C7), an isocyanate derivative, and a rod-shaped compound;

[0008] Wherein, the isocyanate derivative is 1,6-hexamethylene diisocyanate or 3,5-dimethylphenyl isocyanate;

[0009] The structural formula of the rod-shaped compound is:

[0010]

[0011] The present invention uses dibenzo-24-crown-8 and benzo-21-crown-7 as the ring components of the rotaxane mechanical interlocking molecules, uses a rod-shaped compound as the axis component, uses an isocyanate derivative as a blocking group, and uses the hydroxyl group of the rod-shaped compound as a reactive group. Under the condition of not adding a catalyst, the rotaxane mechanical interlocking molecules are prepared by a one-pot method. The method can not only achieve 100% atom economy, meet the requirements of green chemistry, but also achieve a yield of more than 65%, realizing the efficient preparation of rotaxane mechanical interlocking molecules.

[0012] The structural formula of the rotaxane mechanical interlocking molecule is selected from:

[0013] (1) Hetero[5]rotaxane mechanically interlocked molecules:

[0014]

[0015] (2) Hetero[3]rotaxane mechanically interlocked molecules:

[0016]

[0017] Preferably, the molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, isocyanate derivative, and rod-shaped compound is 28-37: 28-37: 9-42: 18-25.

[0018] Further preferably, the molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, 1,6-hexamethylene diisocyanate, and the rod-shaped compound is 33-37: 33-37: 9-11: 21-25; or the molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, 3,5-dimethylphenyl isocyanate, and the rod-shaped compound is 28-32: 28-32: 38-42: 18-22.

[0019] Most preferably, the molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, 1,6-hexamethylene diisocyanate, and the rod-shaped compound is 35:35:10:23; or the molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, 3,5-dimethylphenyl isocyanate, and the rod-shaped compound is 30:30:40:20.

[0020] Preferably, the preparation method is: after dibenzo-24-crown-8, benzo-21-crown-7 and a rod-shaped compound are assembled to form a pseudorotaxane, the pseudorotaxane is capped with an isocyanate derivative to form the rotaxane mechanically interlocked molecule.

[0021] The synthetic route of the rotaxane mechanical interlocking molecule is as follows:

[0022]

[0023] or

[0024]

[0025] More preferably, the assembly temperature is 20-30°C.

[0026] More preferably, the assembly time is 1.8 to 2.2 hours, and most preferably 2 hours.

[0027] More preferably, the end-capping temperature is 20-30°C.

[0028] More preferably, the blocking time is 45 to 50 hours, and most preferably 48 hours.

[0029] Preferably, the reaction is carried out in an organic solvent, wherein the organic solvent is chloroform and acetonitrile in a volume ratio of 4.8 to 5.2: 1. The amount of the organic solvent used is sufficient to dissolve the reaction raw materials.

[0030] Preferably, the reaction is carried out in an inert atmosphere.

[0031] Further preferably, the inert atmosphere is an argon atmosphere, a nitrogen atmosphere or a helium atmosphere.

[0032] Preferably, the reaction is carried out while stirring.

[0033] More preferably, the stirring speed is 500-1000 rpm.

[0034] Preferably, after the reaction, washing, drying and purification are carried out in sequence.

[0035] More preferably, the washing is washing with water.

[0036] More preferably, the washing is performed 3 to 5 times.

[0037] Further preferably, the purification is performed by column chromatography.

[0038] More preferably, the eluent used in the column chromatography method is dichloromethane and methanol in a volume ratio of 19 to 21:1, and most preferably dichloromethane and methanol in a volume ratio of 20:1.

[0039] More preferably, the filler used in the column chromatography is silica gel.

[0040] The present invention has the following beneficial effects:

[0041] 1. The present invention uses dibenzo-24-crown-8 and benzo-21-crown-7 as the ring components of the rotaxane mechanical interlocking molecules, uses a rod-shaped compound as the axis component, uses an isocyanate derivative as a blocking group, and uses the hydroxyl group of the rod-shaped compound as a reactive group. Under the condition of not adding a catalyst, the rotaxane mechanical interlocking molecules are prepared by a one-pot method, thereby avoiding the environmental pollution risk caused by the use of heavy metal catalysts and having industrial feasibility.

[0042] 2. Under the process of the present invention, the yield of rotaxane mechanically interlocked molecules can reach more than 65%, providing an efficient raw material preparation process for the fields of molecular machines, reaction intermediates, catalysts, drug delivery systems, etc.

[0043] 3. The preparation process of the present invention is simple, and the atom economy reaches 100%, which meets the requirements of green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the hetero[5]rotaxane mechanically interlocked molecule obtained in Example 1.

[0045] Figure 2 This is the carbon NMR spectrum of the hetero[5]rotaxane mechanically interlocked molecule obtained in Example 1.

[0046] Figure 3 This is the high-resolution electrospray ionization mass spectrum of the hetero[5]rotaxane mechanically interlocked molecules obtained in Example 1.

[0047] Figure 4 This is the homonuclear hydrogen-hydrogen correlation spectrum of the hetero[5]rotaxane mechanically interlocked molecule obtained in Example 1.

[0048] Figure 5 This is the homonuclear rotating coordinate NOE spectrum of the hetero[5]rotaxane mechanically interlocked molecule obtained in Example 1.

[0049] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the hetero[3]rotaxane mechanically interlocked molecule obtained in Example 4.

[0050] Figure 7 This is the carbon NMR spectrum of the hetero[3]rotaxane mechanically interlocked molecule obtained in Example 4.

[0051] Figure 8 This is the high-resolution electrospray ionization mass spectrum of the hetero[3]rotaxane mechanically interlocked molecules obtained in Example 4.

[0052] Fig. 9 This is the homonuclear hydrogen-hydrogen correlation spectrum of the hetero[3]rotaxane mechanically interlocked molecule obtained in Example 4.

[0053] Fig.10 This is the homonuclear rotation coordinate system NOE spectrum of the hetero[3]rotaxane mechanically interlocked molecule obtained in Example 4.

[0054] Fig.11 This is the hydrogen nuclear magnetic resonance spectrum of the main product point of Comparative Example 1.

[0055] Fig.12 This is the hydrogen nuclear magnetic resonance spectrum of the main product point of Comparative Example 2.

[0056] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of the main product point of Comparative Example 3.

[0057] Fig.14 This is the hydrogen nuclear magnetic resonance spectrum of the main product point of Comparative Example 4.

[0058] Fig.15 This is the hydrogen nuclear magnetic resonance spectrum of the main product point of Comparative Example 5. DETAILED DESCRIPTION

[0059] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0060] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0061] Example 1 A method for preparing a rotaxane-type mechanically interlocked molecule

[0062] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25℃ and 800rpm under argon atmosphere, and then 0.10mmol 1,6-hexanediisocyanate was added, and the mixture was stirred for 48h at 25℃ and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried over anhydrous sodium sulfate for 30min, and then filtered. The filtrate was spin-dried and purified by silica gel column chromatography (eluent was dichloromethane and methanol in a volume ratio of 20:1) to obtain 0.241g yellow solid hetero[5]rotaxane mechanical interlocked molecule (yield 66.8%).

[0063] The structure of the hetero[5]rotaxane mechanically interlocked molecules obtained in this example was characterized:

[0064] (1) H NMR spectroscopy 1 H NMR

[0065] 10.0 mg of hetero[5]rotaxane mechanical interlocked molecules were dissolved in 0.6 mL of deuterated chloroform and measured using a Bruker AV-400 spectrometer. The protons were assigned to the protons and the resulting H NMR spectrum was ( 1 H NMR, CDCl3, 400 MHz, 298 K) Figure 1 shown.

[0066] (2) C NMR spectroscopy 13 C NMR

[0067] 10.0 mg of hetero[5]rotaxane mechanical interlocking molecules were dissolved in 0.6 mL of deuterated chloroform and measured using a Bruker AV-400 spectrometer. The carbon atoms to which they belonged were assigned, and the resulting carbon NMR spectrum was ( 13 C NMR, CDCl3, 100 MHz, 298 K) Figure 2 shown.

[0068] (3) High-resolution electrospray ionization mass spectrometry (HR ESI-MS)

[0069] The molecular weight of hetero[5]rotaxane mechanically interlocked molecules was analyzed using Waters LCT Premier XE high-resolution electrospray ionization mass spectrometry. The high-resolution electrospray ionization mass spectrum is shown in Figure 2. Figure 3 As shown, you can see [M-2PF6] 2+

[0070] (1422.8095), [M-3PF6] 3+(899.7936), [M-4PF6] 4+ (638.6031), [M+8D-8H-2PF6] 2+ (1427.8439), [M+H2O-2PF6] 2+ (1431.7839), [M+6D-6H+H2O-2PF6] 2+ (1434.8253), [M+CH3OH-3PF6] 3+ (911.5356) and other molecular ion peaks.

[0071] (4) Homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1 H COSY

[0072] The homonuclear hydrogen-hydrogen correlation spectra of the mechanically interlocked hetero[5]rotaxane molecules were measured ( 1 H- 1 H COSY, CDCl3, 400MHz, 298K) Figure 4 As shown in the figure, the cross peak CP1 indicates that H d , H f Respectively with H e There is a correlation; the cross peak CP2 indicates that H i With H j There is a correlation; the cross peak CP3 indicates that H k With H j There is a correlation; the cross peak CP4 indicates that the proton H on the B21C7 ring is t There is a correlation; the cross peak CP5 indicates that H o With H n There is a correlation; the cross peak CP6 indicates that H p With H q There is a correlation; the cross peak CP7 indicates that H m With H l There is a correlation.

[0073] (5) NOE spectrum of homonuclear rotating coordinate system HH ROESY

[0074] The homonuclear rotating coordinate NOE spectrum of the mechanically interlocked hetero[5]rotaxane molecules (HH ROESY, CDCl3, 400 MHz, 298 K) was measured as follows: Figure 5 As shown in the figure, the cross peak CP1 indicates that H g , H h There is a spatial correlation with the proton H on the DB24C8 ring, and the cross peak CP2 indicates that H d With H c There is spatial correlation, and the cross peak CP3 indicates that Ho With H r There is a spatial correlation, and the cross peak CP4 indicates that H a With H b There is a spatial correlation. The cross peaks CP5, CP6 and CP7 indicate that the proton H on the B21C7 ring is respectively n , H m There is spatial correlation.

[0075] In summary, combined with H NMR 1 H NMR, carbon nuclear magnetic resonance spectroscopy 13 C NMR, high-resolution electrospray ionization mass spectrometry HRESI-MS, homonuclear hydrino-hydrogen correlation spectroscopy 1 H- 1 The results of H COSY and homonuclear rotating coordinate NOE spectra HH ROESY can confirm that the yellow solid obtained in this example is the hetero[5]rotaxane mechanically interlocked molecule, and its structure is:

[0076]

[0077] The reaction equation of the present embodiment is as follows:

[0078]

[0079] Example 2 Preparation method of a rotaxane mechanically interlocked molecule

[0080] 0.33mmol dibenzo-24-crown-8, 0.33mmol benzo-21-crown-7 and 0.21mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 4.8:1), stirred for 2.2h at 20℃ and 1000rpm under argon atmosphere, then 0.09mmol 1,6-hexane diisocyanate was added, and the mixture was stirred for 50h at 20℃ and 1000rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried over anhydrous sodium sulfate for 25min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (eluent was dichloromethane and methanol in a volume ratio of 19:1) to obtain 0.219g yellow solid hetero[5]rotaxane mechanical interlocked molecule (yield 66.5%).

[0081] This example uses the same method as in Example 1 to measure the H NMR spectrum of the product. 1 H NMR spectrum, C NMR spectrum 13 C NMR, high-resolution electrospray ionization mass spectrometry HR ESI-MS, homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1The H COSY spectrum, the homonuclear rotating coordinate system NOE spectrum and the HH ROESY spectrum confirmed that the structure was the same as that of Example 1.

[0082] Example 3 Preparation method of rotaxane mechanically interlocked molecules

[0083] 0.37 mmol of dibenzo-24-crown-8, 0.37 mmol of benzo-21-crown-7 and 0.25 mmol of rod-shaped compound were dissolved in 6 mL of organic solvent (chloroform and acetonitrile in a volume ratio of 5.2:1), stirred for 1.8 h at 30°C and 500 rpm under argon atmosphere, and then 0.11 mmol of 1,6-hexanediisocyanate was added, and the mixture was stirred for 45 h at 30°C and 500 rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10 mL of deionized water (repeated 5 times), dried over anhydrous sodium sulfate for 35 min, and then filtered. The filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 21:1) to obtain 0.261 g of a yellow solid hetero[5]rotaxane mechanical interlocked molecule (yield 66.6%).

[0084] This example uses the same method as in Example 1 to measure the H NMR spectrum of the product. 1 H NMR spectrum, C NMR spectrum 13 C NMR, high-resolution electrospray ionization mass spectrometry HR ESI-MS, homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1 The H COSY spectrum, the homonuclear rotating coordinate system NOE spectrum and the HH ROESY spectrum confirmed that the structure was the same as that of Example 1.

[0085] Example 4 Preparation method of a rotaxane mechanically interlocked molecule

[0086] 0.30mmol dibenzo-24-crown-8, 0.30mmol benzo-21-crown-7 and 0.20mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25℃ and 800rpm under argon atmosphere, and then 0.40mmol 3,5-dimethylphenylisocyanate was added, and the mixture was stirred for 48h at 25℃ and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried over anhydrous sodium sulfate for 30min, and then filtered. The filtrate was spin-dried and purified by silica gel column chromatography (eluent was dichloromethane and methanol in a volume ratio of 20:1) to obtain 0.236g yellow solid hetero[3]rotaxane mechanical interlocked molecule (yield 72.4%).

[0087] The structure of the hetero[3]rotaxane mechanically interlocked molecules obtained in this example was characterized:

[0088] (1) H NMR spectroscopy 1 H NMR

[0089] 10.0 mg of hetero[3]rotaxane mechanical interlocked molecules were dissolved in 0.6 mL of deuterated chloroform and measured using a Bruker AV-400 spectrometer. The protons were assigned to the protons and the resulting H NMR spectrum was ( 1 H NMR, CDCl3, 400 MHz, 298 K) Figure 6 shown.

[0090] (2) C NMR spectroscopy 13 C NMR

[0091] 10.0 mg of hetero[3]rotaxane mechanical interlocking molecules were dissolved in 0.6 mL of deuterated chloroform and measured using a Bruker AV-400 spectrometer. The carbon atoms to which they belonged were assigned, and the resulting NMR carbon spectrum was ( 13 C NMR, CDCl3, 100 MHz, 298 K) Figure 7 shown.

[0092] (3) High-resolution electrospray ionization mass spectrometry (HR ESI-MS)

[0093] The molecular weight of the hetero[3]rotaxane mechanically interlocked molecules was analyzed using Waters LCT Premier XE high-resolution electrospray ionization mass spectrometry. The high-resolution electrospray ionization mass spectrum is shown in Figure 2. Figure 8 As shown, we can see [M+2D-2H-PF6] + (1486.5176), [M+H2O-PF6] + (1501.4092), [M+CH3OH-2PF6] 2+ (685.4321) and other molecular ion peaks.

[0094] (4) Homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1 H COSY

[0095] The homonuclear hydrogen-hydrogen correlation spectra of the mechanically interlocked hetero[3]rotaxane molecules were measured ( 1 H- 1 H COSY, CDCl3, 400MHz, 298K) Fig. 9 As shown in the figure, the cross peak CP1 indicates that H d , H f Respectively with H e There is a correlation; the cross peak CP2 indicates that H j With H k There is a correlation, CP3 shows that Hv With H w There is a correlation; the cross peak CP4 indicates that H x With H w There is a correlation; the cross peak CP5 indicates that H o With H n There is a correlation; the cross peak CP6 indicates that H k With H l There is a correlation.

[0096] (5) NOE spectrum of homonuclear rotating coordinate system HH ROESY

[0097] The homonuclear rotating coordinate NOE spectrum of the mechanically interlocked hetero[3]rotaxane molecules (HH ROESY, CDCl3, 400MHz, 298K) was measured as follows: Fig.10 As shown in the figure, the cross peak CP1 indicates that H d , H f There is a spatial correlation with the proton H on the aromatic ring of B21C7, and the cross peak CP2 indicates that H d With H c There is spatial correlation, and the cross peak CP3 indicates that H a With H b There is a spatial correlation, and the cross peak CP4 indicates that H w With H r There is a spatial correlation, and the cross peak CP5 indicates that the proton H on the B21C7 ring is connected to H i There is a spatial correlation, and the cross peak CP6 indicates that H k With H i There is a spatial correlation, and the cross peak CP7 indicates that H n With H o There is spatial correlation, and the cross peak CP8 indicates that H u With H o There is a spatial correlation, and the cross peak CP9 indicates that the proton H on the B21C7 ring is connected to H m There is spatial correlation, and the cross peak CP10 indicates that H k With H u There is spatial correlation.

[0098] In summary, combined with H NMR 1 H NMR, carbon nuclear magnetic resonance spectroscopy 13 C NMR, high-resolution electrospray ionization mass spectrometry HRESI-MS, homonuclear hydrino-hydrogen correlation spectroscopy 1 H- 1 The results of H COSY and homonuclear rotating coordinate NOE spectra HH ROESY can confirm that the yellow solid obtained in this example is a hetero[3]rotaxane mechanically interlocked molecule, and its structure is:

[0099]

[0100] The reaction equation of the present embodiment is as follows:

[0101]

[0102] Example 5 Preparation method of a rotaxane mechanically interlocked molecule

[0103] 0.28mmol dibenzo-24-crown-8, 0.28mmol benzo-21-crown-7 and 0.18mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 4.8:1), stirred for 2.2h at 20℃ and 1000rpm under argon atmosphere, then 0.38mmol 3,5-dimethylphenylisocyanate was added, and the mixture was stirred for 50h at 20℃ and 1000rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried over anhydrous sodium sulfate for 25min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (eluent was dichloromethane and methanol in a volume ratio of 19:1) to obtain 0.212g yellow solid hetero[3]rotaxane mechanical interlocked molecule (yield 72.2%).

[0104] This example uses the same method as Example 4 to measure the H NMR spectrum of the product. 1 H NMR spectrum, C NMR spectrum 13 C NMR, high-resolution electrospray ionization mass spectrometry HR ESI-MS, homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1 The H COSY spectrum, the homonuclear rotating coordinate system NOE spectrum and the HH ROESY spectrum confirmed that the structure was the same as that of Example 4.

[0105] Example 6 Preparation method of a rotaxane mechanically interlocked molecule

[0106] 0.32mmol dibenzo-24-crown-8, 0.32mmol benzo-21-crown-7 and 0.22mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5.2:1), stirred for 1.8h at 30℃ and 500rpm under argon atmosphere, and then 0.42mmol 3,5-dimethylphenylisocyanate was added, and the mixture was stirred for 45h at 30℃ and 500rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 5 times), dried over anhydrous sodium sulfate for 35min, and then filtered. The filtrate was spin-dried and purified by silica gel column chromatography (eluent was dichloromethane and methanol in a volume ratio of 21:1) to obtain 0.260g yellow solid hetero[3]rotaxane mechanical interlocked molecule (yield 72.5%).

[0107] This example uses the same method as Example 4 to measure the H NMR spectrum of the product. 1 H NMR spectrum, C NMR spectrum 13 C NMR, high-resolution electrospray ionization mass spectrometry HR ESI-MS, homonuclear hydrogen-hydrogen correlation spectrum 1 H- 1 The H COSY spectrum, the homonuclear rotating coordinate system NOE spectrum and the HH ROESY spectrum confirmed that the structure was the same as that of Example 4.

[0108] Comparative Example 1

[0109] The same as Example 1, except that 3 drops of dibutyltin dilaurate (DBTDL) were added at the same time as 0.10 mmol of 1,6-hexamethylene diisocyanate. That is, the specifics of this comparative example are as follows:

[0110] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25°C and 800rpm under argon atmosphere, then 0.10mmol 1,6-hexanediisocyanate and 3 drops of dibutyltin dilaurate (DBTDL) were added, and stirred for 48h at 25°C and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried with anhydrous sodium sulfate for 30min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 20:1).

[0111] The main product obtained by silica gel column chromatography was characterized by hydrogen nuclear magnetic resonance spectrum. The hydrogen nuclear magnetic resonance spectrum ( 1 HNMR, CDCl3, 400MHz, 298K) Fig.11As shown, it can be seen that the main product obtained in this comparative example does not have a mechanical interlocking structure.

[0112] Comparative Example 2

[0113] The same as Example 1, except that 3 drops of stannous octoate are added at the same time as 0.10 mmol of 1,6-hexamethylene diisocyanate. That is, the specifics of this comparative example are as follows:

[0114] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25°C and 800rpm under argon atmosphere, then 0.10mmol 1,6-hexanediisocyanate and 3 drops of stannous octoate were added, and stirred for 48h at 25°C and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried with anhydrous sodium sulfate for 30min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 20:1).

[0115] The main product obtained by silica gel column chromatography was characterized by hydrogen nuclear magnetic resonance spectrum. The hydrogen nuclear magnetic resonance spectrum ( 1 HNMR, CDCl3, 400MHz, 298K) Fig.12 As shown, it can be seen that the main product obtained in this comparative example does not have a mechanical interlocking structure.

[0116] Comparative Example 3

[0117] The same as Example 1, except that 3 drops of dimethyltin dilaurate were added at the same time as 0.10 mmol of 1,6-hexamethylene diisocyanate. That is, the specifics of this comparative example are as follows:

[0118] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25°C and 800rpm under argon atmosphere, then 0.10mmol 1,6-hexanediisocyanate and 3 drops of dimethyltin dilaurate were added, and stirred for 48h under argon atmosphere at 25°C and 800rpm to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried with anhydrous sodium sulfate for 30min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 20:1).

[0119] The main product obtained by silica gel column chromatography was characterized by hydrogen nuclear magnetic resonance spectrum. The hydrogen nuclear magnetic resonance spectrum ( 1HNMR, CDCl3, 400MHz, 298K) Fig.13 As shown, it can be seen that the main product obtained in this comparative example does not have a mechanical interlocking structure.

[0120] Comparative Example 4

[0121] The same as Example 1, except that 3 drops of dibutyltin diacetate were added at the same time as 0.10 mmol of 1,6-hexamethylene diisocyanate. That is, the specifics of this comparative example are as follows:

[0122] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25°C and 800rpm under argon atmosphere, then 0.10mmol 1,6-hexanediisocyanate and 3 drops of dibutyltin diacetate were added, and stirred for 48h at 25°C and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried with anhydrous sodium sulfate for 30min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 20:1).

[0123] The main product obtained by silica gel column chromatography was characterized by hydrogen nuclear magnetic resonance spectrum. The hydrogen nuclear magnetic resonance spectrum ( 1 HNMR, CDCl3, 400MHz, 298K) Fig.14 As shown, it can be seen that the main product obtained in this comparative example does not have a mechanical interlocking structure.

[0124] Comparative Example 5

[0125] The same as Example 1, except that 3 drops of dimethyltin diacetate were added at the same time as 0.10 mmol of 1,6-hexamethylene diisocyanate. That is, the specifics of this comparative example are as follows:

[0126] 0.35mmol dibenzo-24-crown-8, 0.35mmol benzo-21-crown-7 and 0.23mmol rod-shaped compound were dissolved in 6mL organic solvent (chloroform and acetonitrile in a volume ratio of 5:1), stirred for 2h at 25°C and 800rpm under argon atmosphere, then 0.10mmol 1,6-hexanediisocyanate and 3 drops of dimethyltin diacetate were added, and stirred for 48h at 25°C and 800rpm under argon atmosphere to obtain an organic phase. The organic phase was washed with 10mL deionized water (repeated 3 times), dried with anhydrous sodium sulfate for 30min, filtered, and the filtrate was spin-dried and purified by silica gel column chromatography (the eluent was dichloromethane and methanol in a volume ratio of 20:1).

[0127] The main product obtained by silica gel column chromatography was characterized by hydrogen nuclear magnetic resonance spectrum. The hydrogen nuclear magnetic resonance spectrum ( 1 HNMR, CDCl3, 400MHz, 298K) Fig.15 As shown, it can be seen that the main product obtained in this comparative example does not have a mechanical interlocking structure.

[0128] The aforementioned dibutyltin dilaurate, stannous octoate, dimethyltin dilaurate, dibutyltin diacetate and dimethyltin diacetate are often used to catalyze the preparation of rotaxane mechanical interlocking molecules. However, the present invention uses dibenzo-24-crown-8 and benzo-21-crown-7 as the ring components of the rotaxane mechanical interlocking molecules, a rod-shaped compound as the axis component, an isocyanate derivative as the blocking group, and uses the hydroxyl group of the rod-shaped compound as the reactive group. Unexpectedly, it is found that the process can achieve a yield of more than 65% of rotaxane mechanical interlocking molecules without using a catalyst, which is significantly higher than the process using a catalyst.

[0129] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a rotaxane-based mechanically interlocked molecule, characterized in that: It is obtained by reacting dibenzo-24-crown-8, benzo-21-crown-7, isocyanate derivatives, and rod-shaped compounds; Wherein, the isocyanate derivative is 1,6-hexamethylene diisocyanate or 3,5-dimethylphenyl isocyanate; The structural formula of the rod-shaped compound is:

2. The preparation method according to claim 1, characterized in that: The molar ratio of dibenzo-24-crown-8, benzo-21-crown-7, isocyanate derivative, and rod-shaped compound is 28-37:28-37:9-42:18-25.

3. The preparation method according to claim 1, characterized in that: After dibenzo-24-crown-8, benzo-21-crown-7 and rod-shaped compounds are assembled to form pseudorotaxanes, they are capped with isocyanate derivatives to form the rotaxane-type mechanically interlocked molecules.

4. The preparation method according to claim 3, characterized in that: The assembly temperature is 20-30°C.

5. The preparation method according to claim 3, characterized in that: The assembly time is 1.8 to 2.2 hours.

6. The preparation method according to claim 3, characterized in that: The end-capping temperature is 20-30°C.

7. The preparation method according to claim 3, characterized in that: The end-capping time is 45 to 50 hours.

8. The preparation method according to claim 1, characterized in that: The reaction is carried out in an organic solvent, which is chloroform and acetonitrile in a volume ratio of 4.8 to 5.2:

1.

9. The preparation method according to claim 1, characterized in that: The reaction was carried out under an inert atmosphere.

10. The preparation method according to claim 9, characterized in that: The inert atmosphere is an argon atmosphere, a nitrogen atmosphere or a helium atmosphere.

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