A bromobutyl calix[4]carbazole macrocyclic compound, a preparation method thereof, a bromobutyl calix[4]carbazole crystal material, a preparation method and application thereof

Abstract

The application discloses a bromobutyl calix[4] carbazole macrocyclic compound and a preparation method thereof, a bromobutyl calix[4] carbazole crystal material and a preparation method and application thereof. A novel bromobutyl calix[4] carbazole macrocyclic compound is synthesized, and a high-efficiency and energy-saving toluene and alcohol azeotrope separation method is provided based on the macrocyclic compound. The macrocyclic compound has the advantages of simple synthesis route, high yield and easy separation and purification of products. In the field of adsorption separation, the macrocyclic compound has good adsorption selectivity and structural stability, and provides a novel strategy with practical prospect for toluene and alcohol azeotrope separation. The adsorption separation process is simple to operate, does not need complex equipment or high-energy-consumption steps, is suitable for practical application, has outstanding adsorption performance, the material has high adsorption capacity and high selectivity for toluene, and can realize 100% separation purity.

Description

Technical Field

[0001] This invention relates to the field of adsorption technology, and more specifically, to a bromobutylcalix[4]carbazole macrocyclic compound and its preparation method, bromobutylcalix[4]carbazole crystal material and its preparation method and application. Background Technology

[0002] Since Pedersen's discovery of crown ethers in 1967, artificially synthesized macrocyclic hosts have played a crucial role in supramolecular chemistry, forming the foundation for research on molecular recognition and self-assembly. Starting with crown ethers, traditional macrocyclic hosts such as cyclodextrins, calixarnes, and columnar aromatics have been extensively explored, but their constituent units are relatively simple, limiting their functional expansion and application diversity. In recent years, in addition to classic macrocyclic hosts, research focus has gradually shifted to novel electron-rich macrocyclic hosts composed of various aromatic structural units. For example, the biphenyl […] developed by Li Chunju's research group… n The aromatic hydrocarbon family, by controlling the functional groups and number of structural units, has yielded macrocycles with different conformations and sizes. Compared to traditional macrocyclic hosts, these macrocycles exhibit more interesting host-guest properties and self-assembly behavior. Furthermore, the prism […] reported by Gaeta's group… n Aromatic hydrocarbons are a class of novel macrocyclic hosts composed of five or six methylene-bridged 1,5-naphthalene units. These hosts can encapsulate various aromatic compounds into self-assembled pores, thereby suppressing their own molecular aggregation in the solid state and exhibiting enhanced fluorescence, thus enabling the simultaneous adsorption and detection of aromatic compounds. However, despite the reporting of various macrocyclic hosts over the past few decades, the design and construction of novel macrocyclic hosts with unique structures and special properties remain one of the most important and cutting-edge research topics in supramolecular and macrocyclic chemistry.

[0003] The patent specification with publication number CN113061088A discloses a novel macrocyclic compound, an asymmetric columnar aromatic [5], which achieves highly selective adsorption of dichloromethane from a mixture of halogenated hydrocarbon gases (dichloromethane, trichloromethane, and iodomethane). Experiments show that the selectivity in the mixed gas is 99.1%. The crystal structure shows that dichloromethane molecules are trapped in the cavity of the columnar aromatic hydrocarbon, forming a 1:1 host-guest complex. The synthesis method used in this invention has the advantages of simple operation, readily available raw materials and reagents, and mild conditions. However, the synthesis steps of this material are numerous, which is not conducive to large-scale industrial application; and the potential application scenarios are limited, making it unsuitable for treating complex industrial waste gases.

[0004] The patent specification with publication number CN110438569A discloses a novel macrocyclic material with fluorescence sensing function. This material can specifically detect C4–C6 straight-chain alkyl ketone volatile organic compounds. Its working principle is that after being exposed to the target ketone vapor, the material undergoes an adaptive structural transformation, causing the fluorescence color to change from yellow to green. Moreover, this fluorescence response has significant alkyl chain length selectivity. This invention realizes the visual detection of specific volatile organic compounds. The synthesis is simple and the detection process is easy to operate. However, the core raw material is trifluoromethanesulfonate-based columnar aromatic hydrocarbons[5], which are not commercially available common chemicals. This increases the synthesis threshold and cost of the material to a certain extent, limiting its practical application. Summary of the Invention

[0005] This invention addresses the problem that the synthesis of macrocyclic substrates in existing technologies typically involves cumbersome routes and harsh reaction conditions, which not only increases preparation costs but also often leads to a decrease in the yield of the final product, limiting its large-scale practical application. In addition, some macrocyclic substrates have fewer effective adsorption sites and weaker interaction forces with the adsorbed object, thus affecting their overall adsorption selectivity. Such macrocycles may exhibit insufficient chemical and structural stability during long-term use, especially in complex environments, where irreversible structural transformations or performance degradation are likely to occur, thereby shortening their service life. At the same time, many macrocyclic substrates developed so far are still insufficient in terms of the universality of application scenarios and are difficult to directly adapt to diverse industrial separation needs, which further restricts their transformation from the laboratory to the actual industrial environment. This invention provides a bromobutylcalix[4]carbazole macrocyclic compound and its preparation method, bromobutylcalix[4]carbazole crystal material and its preparation method and application.

[0006] Based on the characteristics of simple synthesis, easy modification, rigid structure and well-defined molecular configuration of carbazole unit, and the unique redox activity and luminescence properties, it is considered an ideal unit for constructing macrocyclic main bodies with novel structure, outstanding performance and application potential. At the same time, in view of the limitations of existing macrocyclic main bodies in synthesis and application, as well as the problems of high energy consumption, complex process and dependence on high-purity desorbent in the current separation technology of toluene and alcohol azeotropes, this invention synthesizes a novel bromobutylcalix[4]carbazole macrocyclic compound, and provides an efficient and energy-saving separation method of toluene and alcohol azeotropes based on this macrocyclic compound. The macrocyclic compound has the advantages of simple route, high yield and easy separation and purification of product in synthesis. In the field of adsorption separation, the macrocyclic compound exhibits good adsorption selectivity and structural stability, providing a new strategy with practical prospects for azeotropic separation.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows:

[0008] A bromobutylcalix[4]carbazole macrocyclic compound, the structural formula of which is shown below: .

[0009] The present invention also discloses a method for preparing the bromobutylcalix[4]carbazole macrocyclic compound as described above, comprising the following steps: Ferric chloride hexahydrate was added to an anhydrous dichloromethane solution containing bromobutylcarbazole and paraformaldehyde and stirred at room temperature. Then, water was added to quench the reaction, the organic phase was separated, dried and distilled under reduced pressure to obtain the crude product. The crude product was purified by column chromatography to obtain the bromobutylcalix[4]carbazole macrocyclic compound. .

[0010] Optionally, the preparation method includes: adding 2.0 mmol of bromobutylcarbazole and 12 mmol of paraformaldehyde to 300 mL of anhydrous dichloromethane solution and mixing at room temperature; then adding 0.4 mmol of ferric chloride hexahydrate to the resulting anhydrous dichloromethane solution containing bromobutylcarbazole and paraformaldehyde and stirring at room temperature for 100-180 min; then adding water to quench the reaction and extracting with dichloromethane; combining the organic phases, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain the crude product; purifying the crude product by column chromatography to obtain the bromobutylcalix[4]carbazole macrocyclic compound.

[0011] Optionally, the eluent used in the column chromatography is a mixture of petroleum ether and dichloromethane in a volume ratio of 10:1.

[0012] The present invention also discloses a method for preparing bromobutylcalix[4]carbazole crystal material, the method comprising: placing a bromobutylcalix[4]carbazole macrocyclic compound in dichloromethane, heating to 30°C to dissolve, then storing the resulting solution overnight at 0°C, filtering and collecting the precipitated crystals, and heating the resulting crystals under vacuum at 120°C for 12 hours to obtain the bromobutylcalix[4]carbazole crystal material; wherein the bromobutylcalix[4]carbazole macrocyclic compound is the bromobutylcalix[4]carbazole macrocyclic compound as described above, or the bromobutylcalix[4]carbazole macrocyclic compound prepared by the above preparation method.

[0013] The present invention also discloses a bromobutylcalix[4]carbazole crystal material prepared by the preparation method described above.

[0014] The present invention also discloses a bromobutylcalix[4]carbazole crystal material prepared by the preparation method described above, or the application of the bromobutylcalix[4]carbazole crystal material described above in the adsorption and separation of toluene and alcohol azeotropes.

[0015] Optionally, the application includes: selectively adsorbing toluene in a mixture of toluene and alcohol using the bromobutylcalix[4]carbazole crystal material to achieve separation of toluene and alcohol; the temperature for selective adsorption of toluene is 25°C. During the adsorption process, the bromobutylcalix[4]carbazole crystal material undergoes a crystal form change. Based on multiple non-covalent interactions, toluene in the mixture forms a host-guest complex with the bromobutylcalix[4]carbazole crystal material. The stoichiometric ratio of toluene to bromobutylcalix[4]carbazole crystal material is 2:1, indicating that one bromobutylcalix[4]carbazole molecule can adsorb two toluene molecules, achieving efficient and highly selective separation of toluene from a mixture of gaseous toluene and alcohol, with a separation efficiency of 100%.

[0016] Optionally, the volume ratio of toluene to alcohol in the mixture of toluene and alcohol is 1:1.

[0017] Optionally, the mixture of toluene and alcohol is a mixture of toluene and alcohol vapors.

[0018] Optionally, the alcohol is at least one of methanol and ethanol.

[0019] Optionally, the application further includes: after selective adsorption of toluene is completed, vacuum heating is used to remove the mixture of toluene and alcohol on the surface of the bromobutylcalix[4]carbazole crystal material, wherein the vacuum heating temperature is 45°C and the vacuum heating time is 30 min.

[0020] Optionally, the application also includes: using vacuum heating to remove toluene molecules adsorbed on the bromobutylcalix[4]carbazole crystal material, thereby regenerating the bromobutylcalix[4]carbazole crystal material.

[0021] Optionally, the desorption time can be adjusted according to the sample volume. Preferably, the vacuum heating temperature is 100~120℃. At this temperature, the adsorbed toluene molecules will be gradually released, while the bromobutylcalix[4]carbazole crystal material is stable, and only the crystal form changes during the desorption process. After desorption, the regenerated bromobutylcalix[4]carbazole crystal material is obtained, which can be used to adsorb and separate mixtures of toluene and alcohol for the next cycle.

[0022] Implementing the embodiments of the present invention will have the following beneficial effects: I. Synthesis and Process: The synthetic route of the bromobutylcalix[4]carbazole macrocyclic compound involved is simple, the reaction conditions are mild, the product is easy to separate and purify, and it has good reproducibility and scale-up potential; the adsorption separation process of toluene and alcohol mixture is simple to operate, without complex equipment or high energy consumption steps, and is suitable for practical application. II. Outstanding Adsorption Performance: The material exhibits high adsorption capacity and high selectivity for toluene, and can achieve 100% separation purity. Attached Figure Description

[0023] Figure 1 The 1H NMR spectrum of the bromobutylcalix[4]carbazole crystal material of Example 1 of this invention.

[0024] Figure 2 The nuclear magnetic carbon spectrum of the bromobutylcalix[4]carbazole crystal material of Example 1 of the present invention.

[0025] Figure 3 The mass spectra of the bromobutylcalix[4]carbazole crystal material of Example 1 of the present invention are shown.

[0026] Figure 4 This is the single crystal structure of the bromobutylcalix[4]carbazole crystal material of Example 1 of the present invention.

[0027] Figure 5 The thermogravimetric curve of the bromobutylcalix[4]carbazole crystal material of Example 1 of the present invention is shown.

[0028] Figure 6 This is the single crystal structure of the bromobutylcalix[4]carbazole crystal material after adsorption of toluene in Example 2 of the present invention.

[0029] Figure 7 The simulated PXRD spectra of the bromobutylcalix[4]carbazole crystal material before and after toluene adsorption in Example 2 of this invention are shown.

[0030] Figure 8 The headspace gas chromatography of the bromobutylcalix[4]carbazole crystal material of Example 3 of the present invention after adsorption of mixed vapors of toluene and methanol.

[0031] Figure 9 The headspace gas chromatography of the bromobutylcalix[4]carbazole crystal material of Example 4 of the present invention after adsorption of mixed vapors of toluene and ethanol. Detailed Implementation

[0032] The present invention will be further described below with reference to specific embodiments, but this does not limit the present invention in any way.

[0033] Example 1 The reaction equation of the bromobutylcalix[4]carbazole macrocyclic compound in this embodiment is shown below. The preparation method includes: adding bromobutylcarbazole (604 mg, 2.0 mmol) and paraformaldehyde (360 mg, 12 mmol) to 300 mL of anhydrous dichloromethane solution and mixing at room temperature, then adding ferric chloride hexahydrate (108 mg, 0.4 mmol) to the anhydrous dichloromethane solution containing bromobutylcarbazole and paraformaldehyde, stirring at room temperature for 100 min, then adding water (150 mL) to quench the reaction, and extracting three times with dichloromethane; combining the organic phases, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain crude product solid; purifying the crude product solid by column chromatography, using a mixed solvent of petroleum ether and dichloromethane with a volume ratio of 10:1 as the eluent to obtain the bromobutylcalix[4]carbazole macrocyclic compound.

[0034] .

[0035] Preparation of bromobutylcalix[4]carbazole crystal material in this embodiment: 1.0 g of bromobutylcalix[4]carbazole macrocyclic compound was placed in 20 mL of dichloromethane and heated to 30 °C to dissolve. The resulting solution was then stored overnight at 0 °C. The precipitated crystals were collected by filtration and then heated under vacuum at 120 °C for 12 h to obtain an activated white powder, denoted as H.

[0036] The characterization data of the product prepared in this embodiment are as follows: H, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J = 8Hz, 8H), 7.25 (d, J = 8 Hz, 8H), 4.27 (t, J = 8 Hz, 8H), 4.22 (s, 8H), 3.34 (t, J =8 Hz, 8H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H). 13 C NMR (400 MHz, CD2Cl2, 293 K) δ (ppm): 139.18, 132.95, 126.87,122.87, 120.22, 108.32, 42.22, 41.80, 33.46, 30.34, 27.66. High-resolution mass spectrometry measurement value m / z: 1256.1831, corresponding to [C 68 H 64 [N4Br4]. Melting range: 184–187℃.

[0037] The single crystal structure and related parameters of bromobutylcalix[4]carbazole crystal materials are as follows: Figure 4 As shown, the obtained bromobutylcalix[4]carbazole has a good crystal structure.

[0038] Thermogravimetric analysis results are as follows Figure 5 As shown, the obtained bromobutylcalix[4]carbazole material has good stability.

[0039] Example 2 Adsorption of toluene, methanol and ethanol by bromobutylcalix[4]carbazole crystal material: Take three 20 mL inoculum bottles and add 1 mL of toluene, methanol and ethanol respectively, named H-Tol, H-MeOH and H-EtOH. Take 20 mg of bromobutylcalix[4]carbazole crystal material prepared in Example 1 and place it in three 5 mL open inoculum bottles. Place the three open 5 mL inoculum bottles in three 20 mL inoculum bottles respectively. Seal the 20 mL inoculum bottles and place them in a 25°C water bath for 24 h. The obtained powder is heated in a vacuum oven at 45°C for 30 min.

[0040] The characterization data of the product prepared in this embodiment are as follows: H-Tol, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J =8 Hz, 8H), 7.25 (d, J = 8 Hz, 8H), 7.19–7.15 (m, 8H), 4.27 (t, J = 8 Hz, 8H),4.22 (s, 8H), 3.34 (t, J = 8 Hz, 8H), 2.36 (s, 5H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H).

[0041] H-MeOH, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J =8 Hz, 8H), 7.25 (d, J= 8 Hz, 8H), 4.27 (t, J = 8 Hz, 8H), 4.22 (s, 8H), 3.34 (t, J = 8 Hz, 8H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H).

[0042] H-EtOH, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J =8 Hz, 8H), 7.25 (d, J = 8 Hz, 8H), 4.27 (t, J = 8 Hz, 8H), 4.22 (s, 8H), 3.34 (t, J = 8 Hz, 8H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H).

[0043] 1 1H NMR results showed that the bromobutylcalix[4]carbazole crystal material had a significant adsorption effect on toluene, but did not adsorb methanol and ethanol.

[0044] Single crystal results are as follows Figure 6 As shown, compared with the original single-crystal structure of the bromobutylcalix[4]carbazole crystal material, the structure of the bromobutylcalix[4]carbazole crystal material after adsorbing toluene has changed significantly, indicating that its unit cell parameters have changed. Furthermore, the stoichiometric ratio of the host-guest complex is 1:2, indicating that one bromobutylcalix[4]carbazole molecule can adsorb two toluene molecules.

[0045] The simulation results of PXRD are as follows Figure 7 As shown, compared with the original PXRD spectrum of the bromobutylcalix[4]carbazole crystal material, the PXRD spectrum of the bromobutylcalix[4]carbazole crystal material after adsorbing toluene changed, which indicates that the bromobutylcalix[4]carbazole crystal material adsorbed toluene.

[0046] Example 3 Bromobutylcalix[4]carbazole crystal material with a 1:1 ratio to toluene and methanol v : vAdsorption of the mixture: Take a 20 mL culture bottle, add 0.5 mL toluene and 0.5 mL methanol, named H-Tol / MeOH, take 20 mg of bromobutylcalix[4]carbazole crystal material prepared in Example 1 and place it in a 5 mL open culture bottle, place the open 5 mL culture bottle in the above 20 mL culture bottle, seal the 20 mL culture bottle, place it in a 25 ℃ water bath for 36 h, and heat the obtained powder in a vacuum oven at 45 ℃ for 30 min.

[0047] The characterization data of the product prepared in this embodiment are as follows: H-Tol / MeOH, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J = 8 Hz, 8H), 7.25 (d, J = 8 Hz, 8H), 7.19–7.15 (m, 8H), 4.27 (t, J = 8 Hz,8H), 4.22 (s, 8H), 3.34 (t, J = 8 Hz, 8H), 2.36 (s, 5H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H).

[0048] exist 1 The H NMR spectrum only showed signals of hydrogen atoms belonging to toluene, indicating that the bromobutylcalix[4]carbazole crystal material can selectively adsorb toluene from a mixture of toluene and methanol.

[0049] The results of headspace gas chromatography are as follows Figure 8 As shown, the results indicate that bromobutylcalix[4]carbazole crystal material can selectively adsorb toluene from a mixture of toluene and methanol with a selectivity of up to 100%.

[0050] Example 4 Bromobutylcalix[4]carbazole crystal material with a 1:1 ratio of toluene and ethanol v : v Adsorption of the mixture: Take a 20 mL culture bottle, add 0.5 mL toluene and 0.5 mL ethanol, named H-Tol / EtOH, take 20 mg of bromobutylcalix[4]carbazole crystal material prepared in Example 1 and place it in a 5 mL open culture bottle, place the open 5 mL culture bottle in the above 20 mL culture bottle, seal the 20 mL culture bottle, place it in a 25 ℃ water bath for 36 h, and heat the obtained powder in a vacuum oven at 45 ℃ for 30 min.

[0051] The characterization data of the product prepared in this embodiment are as follows: H-Tol / EtOH, 1 H NMR (400 MHz, CDCl3, 293 K) δ (ppm): 7.68 (s, 8H), 7.33 (dd, J = 8 Hz, 8H), 7.25 (d, J = 8 Hz, 8H), 7.19–7.15 (m, 8H), 4.27 (t, J = 8 Hz,8H), 4.22 (s, 8H), 3.34 (t, J = 8 Hz, 8H), 2.36 (s, 5H), 2.05–1.97 (m, 8H), 1.91–1.84 (m, 8H).

[0052] exist 1 The H NMR spectrum only showed signals of hydrogen atoms belonging to toluene, indicating that the bromobutylcalix[4]carbazole crystal material can selectively adsorb toluene from a mixture of toluene and ethanol.

[0053] The results of headspace gas chromatography are as follows Figure 9 As shown, the results indicate that bromobutylcalix[4]carbazole crystal material can selectively adsorb toluene from a mixture of toluene and ethanol with a selectivity of up to 100%.

[0054] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the inventive concept, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A bromobutylcalix[4]carbazole macrocyclic compound, characterized in that, The structural formula of the bromobutylcalix[4]carbazole macrocyclic compound is shown below: 。 2. A method for preparing the bromobutylcalix[4]carbazole macrocyclic compound as described in claim 1, characterized in that, Includes the following steps: Ferric chloride hexahydrate was added to an anhydrous dichloromethane solution containing bromobutylcarbazole and paraformaldehyde and stirred at room temperature. Then, water was added to quench the reaction, the organic phase was separated, dried and distilled under reduced pressure to obtain the crude product. The crude product was purified by column chromatography to obtain the bromobutylcalix[4]carbazole macrocyclic compound. 。 3. The method for preparing the bromobutylcalix[4]carbazole macrocyclic compound according to claim 2, characterized in that, The preparation method includes: adding 2.0 mmol of bromobutylcarbazole and 12 mmol of paraformaldehyde to 300 mL of anhydrous dichloromethane solution and mixing at room temperature; then adding 0.4 mmol of ferric chloride hexahydrate to the anhydrous dichloromethane solution containing bromobutylcarbazole and paraformaldehyde and stirring at room temperature for 100-180 min; then adding water to quench the reaction and extracting with dichloromethane; combining the organic phases, drying with anhydrous sodium sulfate, and distilling under reduced pressure to obtain the crude product; purifying the crude product by column chromatography to obtain the bromobutylcalix[4]carbazole macrocyclic compound.

4. The method for preparing the bromobutylcalix[4]carbazole macrocyclic compound according to claim 2, characterized in that, The column chromatography used a mixed solvent of petroleum ether and dichloromethane in a volume ratio of 10:1 as the eluent.

5. A method for preparing a bromobutylcalix[4]carbazole crystal material, characterized in that, The preparation method includes: placing the bromobutylcalix[4]carbazole macrocyclic compound in dichloromethane, heating to 30°C to dissolve, then storing the resulting solution overnight at 0°C, filtering and collecting the precipitated crystals, and heating the resulting crystals under vacuum at 120°C for 12 hours to obtain the bromobutylcalix[4]carbazole crystal material; the bromobutylcalix[4]carbazole macrocyclic compound is the bromobutylcalix[4]carbazole macrocyclic compound as described in claim 1, or the bromobutylcalix[4]carbazole macrocyclic compound prepared by the preparation method described in any one of claims 2-4.

6. A bromobutylcalix[4]carbazole crystal material prepared by the preparation method as described in claim 5.

7. A bromobutylcalix[4]carbazole crystal material prepared by the preparation method as described in claim 5, or the application of the bromobutylcalix[4]carbazole crystal material as described in claim 6 in the adsorption and separation of toluene and alcohol azeotropes.

8. The application according to claim 7, characterized in that, The application includes: selectively adsorbing toluene in a mixture of toluene and alcohol using the bromobutylcalix[4]carbazole crystal material to achieve separation of toluene and alcohol; the temperature for selective adsorption of toluene is 25°C.

9. The application according to claim 7, characterized in that, The volume ratio of toluene to alcohol in the mixture of toluene and alcohol is 1:

1.

10. The application according to claim 7, characterized in that, The mixture of toluene and alcohol is a mixture of toluene and alcohol vapors; The alcohol is at least one of methanol and ethanol.

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