CN103373892B - Three-dimensional nanometer graphene based on triptycene and preparation method thereof - Google Patents

Abstract

The invention discloses three-dimensional nanometer graphene based on triptycene and a synthetic method thereof. The three-dimensional nanometer graphene based on the triptycene is a novel coronene-modified triptycene derivative. The preparation method comprises the following steps of: firstly carrying out a Sonogashira coupling reaction on triiodo triptycene to obtain a tri-acetenyl triptycene derivative; then carrying out a Diels-Alder reaction on the tri-acetenyl triptycene derivative to obtain a coronene triptycene derivative; finally carrying out an FeCl3 oxidation and cyclization reaction in an organic solvent (dichloromethane) under the conditions of gas protection (Ar) and normal temperature for 15-240 minutes to obtain the three-dimensional nanometer graphene based on the triptycene. The preparation method disclosed by the invention is novel and higher in yield. The prepared three-dimensional nanometer graphene based on the triptycene disclosed by the invention has an outstanding effect on the aspect of cell imaging.

Description

A kind of triptycene-based three-dimensional nano-graphene and preparation method thereof

technical field

The invention belongs to the field of chemistry and relates to three-dimensional nanometer graphene.

Background technique

Since 1942, Bartlett et al. (J.Am.Chem.Soc., 1942, 64, 2649.) started from anthracene for the first time, and obtained a new type of compound-triptycene (triptycene) through multi-step reaction synthesis. , the synthesis and research of triptycene and its derivatives have aroused widespread interest. The unique three-dimensional rigid structure and unique photoelectric properties of triptycene and its derivatives make it widely used in many fields such as molecular machines, material chemistry and supramolecular chemistry.

Hexa-peri-hexabenzocoronenes (HBC for short) is a unit system with super large electron conjugation formed by 13 benzene rings. Initially by Clar et al. (Proc.Chem.Soc.1958, 150) after dibenzo-peri-naphthene bromination, under heating conditions through its own coupling and further heating dehydrogenation, a yellow solid compound finally synthesized - six Benzocorone. Due to its high-density electron system and strong π-π conjugation characteristics, this compound can be used as an excellent electron acceptor and has great advantages in the field of supramolecular chemistry. , high thermal stability, excellent electron delocalization performance, and also has great potential applications in conductive materials.

However, there is no report about using triptycene as a skeleton and modifying it with hexabenzocoronene to obtain a new three-dimensional nano-graphene derivative based on triptycene and its synthesis method.

Contents of the invention

The task of the present invention is to provide a kind of triptycene-based three-dimensional nano graphene and preparation method thereof,

Realize the technical scheme of the present invention is: three-dimensional nano-graphene based on triptycene provided by the invention has structure shown in following formula (I),

where R=H or t-bu.

The preparation method of the above-mentioned three-dimensional nano-graphene based on triptycene, comprises the following steps:

Step 1: the compound 2,6,14-triiodotriptycene shown in the following formula IV and the compound phenylacetylene or tert-butylphenylacetylene shown in the following formula II are added to the organic solvent triethylamine, and the Pd (PPh ₃ ) ₄ /CuI as a catalyst, under the condition of inert gas protection, react at 70-80°C for 1-36 hours to obtain the compound triphenylethynyl triptycene derivative shown in the following formula V, compound 2, 6, The molar ratio of 14-triiodotriptycene (IV) to the compound phenylacetylene or tert-butylphenylacetylene, Pd(PPh ₃ ) ₄ , and CuI is 1:3.14:0.15:0.25;

Step 2: Add the triphenylethynyl triptycene derivative obtained in step 1 and the compound tetraphenylcyclopentadienone compound shown in the following formula III in an organic solvent (diphenyl ether), and in an inert gas (Ar) Under protected conditions, react at 260°C for 0.5-72 hours to obtain the compound hexabenzobenzotristycene derivative shown in the following formula VI, the compound triphenylethynyl triptycene derivative and the compound tetraphenylcyclopentadienone The molar ratio of the compound is 1: 3.25;

Step 3: Add the hexabenzocenetriptycene derivative obtained in Step 2 into an organic solvent (dichloromethane), under the protection of an inert gas, add _FeCl solution dissolved in nitromethane, and react at room temperature for 15-240min The triptycene-based three-dimensional nano-graphene was obtained, and the molar ratio of the compound hexabenzocene triptycene derivative (VI) to _FeCl3 was 1:64.50.

The reaction time of the above step 3 is 15-240min, and the reaction temperature of the above step 3 is 25-45°C.

The triptycene-based three-dimensional nano-graphene product obtained by the above preparation method is purified by column chromatography and recrystallization.

The synthetic route of the present invention is as follows:

The triptycene-based three-dimensional nano-graphene provided by the invention has strong fluorescent properties and has a remarkable effect in cell imaging.

The following compounds are referred to in this patent application:

In this patent application, compound II is named as phenylethynyl compound; compound III is named as tetraphenylcyclopentadienone compound; compound IV is named as 2,6,14-triiodotriptycene; The compound V is named triphenylethynyl triptycene derivative; the compound VI is named hexabenzocene triptycene derivative.

The present invention has following characteristics:

(1) The derivatives of hexaphenylbenzenetriptycene are dehydrogenated by _FeCl3 cyclodehydrogenation at room temperature under the protection of argon to obtain a new three-dimensional nano-graphene derivative based on triptycene, with a high yield of 78%-90% , and the reaction conditions are simple and mild.

(2) The compounds synthesized by this method can be separated by column chromatography, using silica gel as the stationary phase, and the eluent can be selected from dichloromethane-petroleum ether, ethyl acetate-petroleum ether, tetrahydrofuran-petroleum ether, dichloromethane -N-hexane, ethyl acetate-n-hexane and other mixed solvents.

(3) The synthesized triptycene-based novel three-dimensional nano-graphene derivative has a novel structure and has not yet been prepared. The present invention organically combines the three-dimensional rigid structure of triptycene with the high π-π conjugated system of hexabenzocoronene to construct a new nano-graphene derivative with a three-dimensional structure, because it has strong fluorescence properties , which has a remarkable effect in cell imaging.

Description of drawings

Fig. 1 three-dimensional nano-graphene (R=t-Bu) structural formula;

Fig. 2 Fluorescence imaging diagram of co-incubation of three-dimensional nano-graphene (R=t-Bu) and HepG2 liver cancer cells.

Detailed ways

In order to better understand the present invention, the present invention will be further described in detail below in conjunction with examples, but the scope of protection claimed by the present invention is not limited to the scope described in examples.

Embodiment 1 2,6, the synthesis of 14-triphenylethynyl triptycene

Add 200mg triiodotriptycene (0.315mmol), 37mg Pd(PPh ₃ ) ₄ (0.036mmol) and 11.6mgCuI (0.061mmol) into a 100ml two-necked bottle, blow argon, add 200ul phenylacetylene (0.99mmol) and 40ml of triethylamine, then stirred and refluxed at 70°C, stopped the reaction after 48 hours, added dichloromethane to dissolve, successively washed with dilute hydrochloric acid solution, water, extracted with dichloromethane, dried over anhydrous Na ₂ SO ₄ , passed through the column Chromatography, using dichloromethane-petroleum ether (1:3) as the eluent, afforded 2,6,14-triphenylethynyl triptycene as a white solid.

Yield: 68.0%. Melting point: 184-185°C

¹ H NMR (400MHz, CDCl ₃ ): δ5.45(s, 1H), 5.46(s, 1H), 7.25(dd, J=7.6, 1.2Hz, 3H), 7.33-7.37(m, 9H), 7.40 (d, J=7.6Hz, 3H), 7.50-7.53 (m, 6H), 7.60 (d, J=1.2Hz, 3H). ¹³ CNMR (100MHz, CDCl ₃ ): δ53.41, 53.50, 88.77, 89.40 , 120.39, 120.42, 123.32, 123.77, 123.80, 126.86, 128.16, 128.31, 129.09, 131.58, 144.47, 144.49, 144.51, 144.57. EI-MS: m/z555 (M+). Anal. Calcd ₂₆ for C ₄ , 95.28; H, 4.72; Found: C, 95.01; H, 5.08.

Example 2 Synthesis of 2,6,14-tri-tert-butylphenylethynyl triptycene

Add 200mg of triiodotriptycene (0.315mmol), 37mg of Pd(PPh ₃ ) ₄ (0.036mmol) and 11.6mg of CuI (0.061mmol) into a 100ml two-necked flask, blow argon, and add 178ul of p-tert-butylphenylacetylene (0.99mmol) and 40ml triethylamine, then stirred and refluxed at 70°C, stopped the reaction after 24 hours, added dichloromethane to dissolve, successively washed with dilute hydrochloric acid solution, water, extracted with dichloromethane, anhydrous Na ₂ SO ₄ After drying, column chromatography with dichloromethane-petroleum ether (1:10) was used as the eluent to obtain 2,6,14-tri-tert-butylphenylethynyltriptycene as a white solid product.

Yield: 70.4%. Melting point: 190-193°C

¹ H NMR (400MHz, CDCl ₃ ): δ1.310(s, 9H), 5.404(s, 1H), 5.413(s, 1H), 7.210(dd, J=2.8, 2.8Hz, 3H), 7.335-7.355 (m, 9H), 7.421 (d, J=8HZ, 6H), 7.556 (s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δ29.50, 29.67, 30.31, 31, 17, 34.77, 38.97, 53.38, 53.47, 88.77, 88.86, 120.28, 120.58, 123.70, 125.31, 126.81, 128.98, 131.29, 144.35, 144.48, 151.41. EI-MS: m/z 723 (M+). Anal. Calcd for C ₅₀ : C H ₅ , 93.03; H, 6.97; Found: C, 93.38; H, 6.61.

Example 3 Synthesis of 2,6,14-three (2,3,4,5,6-pentaphenyl)-phenyl triptycene

100mg of triphenylethynyl triptycene (0.181mmol), 215mg of tetraphenylcyclopentadienone (0.560mmol) and 1.5ml of diphenyl ether were heated and stirred at 260°C under the protection of argon to react after 48 hours completely. After column chromatography, dichloromethane-petroleum ether (1:3) was used as the eluent to obtain a yellow solid 2,6,14-tris(2,3,4,5,6-pentaphenyl)-phenyltris pterene.

Yield: 52.0%. Melting point: >300°C

2,6,14-tris(2,3,4,5,6-pentaphenyl)-phenyl triptycene

¹ H NMR (400MHz, CDCl ₃ ): δ4.05(s, 1H), 4.28(s, 1H), 6.29-6.36(m, 9H), 6.48-6.61(m, 9H), 6.72-6.82(m, 66h). ¹³ C NMR (100MHz, CDCL ₃ ): Δ52.79, 53.00, 121.63, 125.02, 125.10, 125.30, 126.10, 126.36, 126.73, 127.96, 129.89.29.9.29.96, 129.09.13, 129.09.09.13,29.09.96.29. ，131.44，131.58，131.64，131.72，135.84，136.28，139.73，140.04，140.12，140.19，140.23，140.33，140.37，140.40，140.46，140.49，140.68，140.72，140.78，140.82，142.36，143.14，143.66，143.89.MALDI - TOF-MS: m/z 1647 (M+Na+), 1663 (M+K+). Anal. Calcd for C ₁₂₈ H ₈₆ : C, 94.66; H, 5.34; Found: C, 95.02; H, 5.50.

Example 4 Synthesis of 2,6,14-three (2,3,4,5,6-penta-tert-butylphenyl)-phenyl triptycene

With 130mg 4-tert-butyl-triphenylethynyl triptycene (0.181mmol), 215mg tetra-4-tert-butylphenyl-cyclopentadienone (0.560mmol) and 1.5ml diphenyl ether, argon protection, The reaction was heated and stirred at 260°C, and the reaction was complete after 48 hours. The eluent was dichloromethane-petroleum ether (1:9), and the yellow solid 2,6,14-tri(2,3,4,5,6-penta-tert-butylphenyl)-benzene was obtained by column chromatography base triptycene.

Yield: 43.0%. Melting point: >300°C

2,6,14-tris(2,3,4,5,6-penta-tert-butylphenyl)-phenyl triptycene

¹ H NMR (400MHz, CDCl ₃ ): δ1.068-1.116(m, 135H), 4.239(s, 1H), 4.422(s, 1H), 6.168(d, J=7.6HZ, 9H), 6.353(d , J=7.6HZ, 6H), 6.542-6.899 (m, 54H). ¹³ C NMR (100MHz, CDCl ₃ ): δ52.79, 53.04, 118.89, 120.47, 120.78, 122.99, 123.22, 126.37, 126.56, 128.27, 129.74，131.13，131.21，136.63，137.77，138.05，138.18，139.88，140.21，140.35，140.56，142.29，143.04，143.48，143.99，147.24，147.34，147.44，157.25.MALDI-TOF-MS：2466(M+).Anal .Calcd for C ₁₈₈ H ₂₀₆ : C, 91.58; H, 8.42; Found: C, 91.02; H, 8.50.

Example 5 Synthesis of three-dimensional nano-graphene (R=H)

Add 150mg of 2,6,14-tris(2,3,4,5,6-pentaphenyl)-phenyltriptycene (0.082mmol) and 70ml of dichloromethane into a 150ml two-necked bottle, and blow in argon, Then nitromethane ( _5ml ) solution of 882mg FeCl3 (5.292mmol) was slowly added in the two-necked flask, stirred at normal temperature, stopped the reaction after reacting for 70min, collected the precipitate by filtration, washed with methanol, and dried to obtain a brown solid product. The product is insoluble in common organic solvents.

Yield: 76.0%. Melting point: >300°C

MALDI-TOF-MS: m/z 1588 (M+), 1611 (M+Na+). Anal. Calcd for C128H50: C, 96.83; H, 3.17; Found: C, 97.02; H, 2.89.

Example 6 Synthesis of three-dimensional nano-graphene (R=t-bu)

Add 205mg 2,6,14-tris(2,3,4,5,6-penta-tert-butylphenyl)-phenyl triptycene (0.082mmol) and 70ml dichloromethane into a 150ml two-necked bottle, pass Inject argon, then slowly add nitromethane (5ml) solution of 882mg FeCl3 (5.292mmol) in the two-necked flask, stir at normal temperature, stop the reaction after reacting for 125min, remove the solvent under reduced pressure, dissolve with dichloromethane, wash to remove FeCl3, dichloromethane extraction. After column chromatography, dichloromethane-petroleum ether (1:9) was used as the eluent, and yellow three-dimensional nano-graphene (R=t-Bu) was obtained after recrystallization.

Yield: 87.0%. Melting point: >300°C

¹ H NMR (400MHz, CDCl ₃ ): δ1.38(s, 18H), 1.73(s, 9H), 1.75-1.76(d, 27H), 1.787-1.797(d, 27H), 1.876(s, 45H) , 1.899(s, 45H), 2.307(s, 9H), 8.234(s, 1H), 8.886(s, 1H), 9.179-9.348(m, 25H), 9.462(s, 3H), 9.517(s, 1H ), 9.721(s, 1H)), 9.816(d, J=10.4HZ, 3H). ¹³ C NMR (100MHz, CDCl ₃ ): δ31.85, 31.96, 32.00, 32.04, 32.13, 32.31, 32.39, 32.83, 35.40，35.66，35.71，35.75，35.85，35.95，36.36，52.70，53.30，118.93，119.98，120.46，120.56，120.62，120.73，123.86，123.99，125.28，128.87，130.13，130.22，130.46，130.54，140.64，145.94， 149.00, 149.13, 149.31. MALDI-TOF-MS: m/z 2426 (M ⁺ ). Anal. Calcd for C ₁₂₈ H ₈₆ : C, 92.95; H, 7.05; Found: C, 92.62; H, 7.28.

Example 7 The cell imaging experiment of three-dimensional nano-graphene (R=t-bu):

We select the three-dimensional nano-graphene (R=t-Bu) prepared in Example 6 for use, its structural formula is shown in Fig. 1, first this graphene compound is dissolved in tetrahydrofuran, is mixed with the tetrahydrofuran solution that concentration is 0.2mg/ml, simultaneously Pluronic F68 (poly(ethylene glycol)-block-poly(propyleneglycol)-block-poly(ethylene glycol) was dissolved in water to prepare an aqueous solution with a concentration of 1mg/ml. Take 0.5ml of graphene compound tetrahydrofuran solution and add it dropwise to 5ml In the aqueous solution of pluronic F68, then rotary steamed to remove THF, and finally dilute to 10ml with water to obtain nanoparticles. Carry out cell imaging research with this sample, the specific operation is: after HepG2 liver cancer cells are sliced for 24 hours, add the sample containing Culture medium (the concentration of F68 is 500ug/ml, the concentration of graphene compound is 10ug/ml), incubate at 37°C for 0.5h, 1.5h, 3h, wash with cold pbs three times, fix with 4% paraformaldehyde for 20min. Mount the slide in glycerol pbs, and take a film with a laser confocal microscope (488nm laser excitation, 525nm emission filter, exposure 2s). The results show (see Figure 2), as time increases, the fluorescence of the cell increases, indicating that the nanoparticle enters the cell The content gradually increases with time effect. The results show that this triptycene-based three-dimensional nano-graphene has strong fluorescence properties and has a significant effect in cell imaging.

Claims (7)

1., based on a three-dimensional manometer Graphene for triptycene, there is structure shown in formula I,

2. according to claim 1 have with the preparation method of the three-dimensional manometer Graphene based on triptycene of structure shown in following formula I,

Comprise the following steps:

Step one: by with compound 2,6, the 14-tri-iodo triptycene shown in following formula IV with join in organic solvent triethylamine, with Pd (PPh with the compound phenylacetylene shown in Formula Il or tert.-butylbenzene acetylene ₃) ₄/ CuI is catalyzer, and under the condition of protection of inert gas, 70-80 DEG C of reaction obtains with the compound three phenylacetylene base triptycene derivative shown in following formula V for 1-36 hour;

Step 2: the compound tetraphenylcyclopentadienone compounds shown in step one gained three phenylacetylene base triptycene derivative and following formula III is added in organic solvent phenyl ether; under the condition of protection of inert gas; 260 DEG C of reactions obtain with the compound coronene triptycene derivative shown in following formula VI for 0.5-72 hour

Step 3: add in organic solvent dichloromethane by step 2 gained coronene triptycene derivative, under the condition of protection of inert gas, adds the FeCl dissolved with Nitromethane 99Min. ₃solution, normal-temperature reaction 15-240min obtains the three-dimensional manometer Graphene based on triptycene.

3. the preparation method of the three-dimensional manometer Graphene based on triptycene according to claim 2, is characterized in that, in step one, and compound 2,6,14-tri-iodo triptycene and compound phenylacetylene or tert.-butylbenzene acetylene, Pd (PPh ₃) ₄, CuI mol ratio be 1: 3.14: 0.15: 0.25.

4. the preparation method of the three-dimensional manometer Graphene based on triptycene according to claim 2, is characterized in that, in step 2, the mol ratio of compound three phenylacetylene base triptycene derivative and compound tetraphenylcyclopentadienone compounds is 1: 3.25.

5. the preparation method of the three-dimensional manometer Graphene based on triptycene according to claim 2, is characterized in that, in step 3, and compound coronene triptycene derivative and FeCl ₃mol ratio be 1: 64.50.

6. the preparation method of the three-dimensional manometer Graphene based on triptycene according to claim 2, is characterized in that, the rare gas element described in step one to three is Ar or nitrogen.

7. the preparation method of the three-dimensional manometer Graphene based on triptycene according to claim 2, is characterized in that the three-dimensional manometer Graphene of gained based on triptycene is through column chromatography and recrystallization purifying.