KR20070049466A - Novel vinyl-substituted metallocorrole catalysts and method theirof - Google Patents

Abstract

The present invention relates to a metal-corrol catalyst substituted with a vinyl group from a corol compound and a method for preparing the same. More specifically, it has a vinyl group comprising the step of preparing a macrocyclic corrol compound consisting of four pyrrole having a vinyl group, and introducing a metal into the center of the corrol compound having one vinyl group at the meso position of the 10th carbon It relates to a metallocorrole catalyst and a method for preparing the same.

The metal-corrole catalyst having a vinyl group of the present invention is capable of binding to biomolecules through chemisorption and reaction with cysteine groups on the surface of the silica modified with thiol groups through the vinyl group. In addition, the present invention can be easily synthesized metal-corrole material in which the vinyl-phenyl group is introduced from a cheap raw material, and the functionalities such as vinyl groups are useful for selecting many kinds of shrinked metal-porphyrins from the viewpoint of oxygen atom transfer reaction. Therefore, it is expected to contribute to researches related to the operation of (non) homogeneous catalytic chemistry, surface chemistry and bioenzyme, and the development of new drugs of specific functionality.

Description

Novel Vinyl-substituted Metallocorrole Catalysts and Method Theirof}

Figure 1 shows the results of the catalytic reaction of the present invention.

The present invention relates to a metal-corrol catalyst substituted with a vinyl group from a corol compound and a method for preparing the same. More specifically, preparing a macrocyclic corrol compound consisting of four pyrroles having a vinyl group, and introducing a divalent metal or a trivalent metal into the center thereof, and preparing a metal-corrole having a vinyl group. It is about a method.

Corol molecules of major interest in the present invention can be easily found in nature as a substance having a structural similarity to porphyrin well known as a macromolecule. Examples include corin present in vitamin B ₁₂ that binds cobalt, and porphyrins in the heme structure that binds iron.

Corrole lacks one mechyl group (-CH: methyne methine or methine) compared to porphyrin, which causes the space formed in the center to be constricted than porphyrin. The constricted space has a characteristic of stabilizing metal ions having a relatively high oxidation number of 3+.

It has been suggested that porphyrins and metal-porphyrins can be used as co-factors together with catalysts or oxidants in various types of reduction reactions as well as oxygen carriers, electron transporters. However, although studies on porphyrins that have structural similarities with corrols have been actively conducted to date, since corrols have different characteristics from porphyrins, research on corols and corol derivatives and metal-corrols is still insufficient. to be. The reason for this is that the method for synthesizing corrol is difficult, and the fact that various applications have not been developed is also because the basic research on the synthesis of corrol was difficult.

This is reflected in the fact that in the 1990s, thirty years after the first publication of corrols, a study of the meso position-substituted corrols was published. Among them, Z. Gross and colleagues published a relatively practical method for synthesizing corol in 1999, and it was easy to make various corol derivatives and metal-corols. In the same year, Gross and colleagues also reported for the first time reactions involving metal-corrole compounds as catalysts ( Chemical Communications 1999, 599). However, it has been pointed out that some specific reactions are not stable as catalysts and are less efficient than conventional metal-porphyrin systems. To date, studies on corol or corol derivatives and metal-corol have been synthesized and coordinated. It has been confined to the content of coupling, and significant results on applicability are lacking.

The present invention relates to a method for stably and easily preparing a new metal-corol substituted with a vinyl group capable of acting as a catalyst in an oxidation reaction, and a catalyst applicability of the material. The technical problem to be achieved through the present invention is first; Preparing a vinyl substituted with a vinyl group, secondly; A divalent metal or a trivalent metal is introduced into the core of the co-roll to prepare a stabilized metal-co-roll catalyst and to reveal the catalytic properties of the compound. In addition, the present invention proposes a technique for preparing a new metal-corrole catalyst substituted with a vinyl group.

The present invention provides a metal-corol catalyst having a vinyl group in which a divalent metal or a trivalent metal is introduced at its center, and a method for producing the same, firstly, preparing a vinyl substituted with a vinyl group and secondly, a new metal having a vinyl group by introducing a metal. It consists of preparing the corrols. The metal-corol substituted with the vinyl group of this invention is represented by following General formula (1).

[Formula 1]

In each step of the present invention, 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole and 5,15-di (pentafluorophenyl) 10- (3-vinylphenyl) corrole and divalent metals thereof are respectively used. Iron, copper, zinc, trivalent metals to provide a metal-co-roll combined with any one selected from iron, manganese, cobalt, chromium, gallium, ruthenium, indium, and more detailed manufacturing method will be described in detail through the examples. .

The metal-corrole materials provided in the present invention are substituted with thiophene groups at the 5th and 15th carbon positions, vinyl-phenyl groups are substituted at the 10th carbon sites, or pentafluoro groups are substituted at the 5th and 15th carbon positions. The vinyl-phenyl group is substituted at the 10th carbon position.

As representative applications of these materials, the present invention intends to disclose a catalytic reaction, and the catalytic reactions to which the above materials can be applied include epoxidation of olefins, hydroxylation of alkanes, and alkene. It can be used for oxidation reactions such as cyclopropanation of alkenes.

In the present invention, the catalytic action of Fe-Corol in the oxidation reaction of styrene and iodosilbenzene will be described in detail through the examples.

In Example 1 of the present invention, 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole; [H ₃ (3DT-10VC)]

In Example 2, 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole; [H ₃ (PFP-10VC)]

Example 3 includes Iron (IV) 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole chloride; Fe (3DT-10VC) Cl

Example 4 includes Iron (IV) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole chloride; Fe (PFP-10VC) Cl

Example 5 includes Copper (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole; Cu (PFP-10VC)

Example 6 includes Cobalt (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole bispyridine; Co (PFP-10VC) 2py

Example 7 includes Manganese (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole; Mn (PFP-10VC)

The manufacturing method of this is disclosed.

The above materials were characterized by ¹ H-NMR, ¹³ C-NMR, and single crystal X-ray diffraction analysis. In addition, experiments on the catalytic applicability of the materials will be described in more detail with reference to Examples.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

<Example 1>

5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole; How to prepare [H ₃ (3DT-10VC)]

5 (3-thienyl) dipyrromethane (1g, 4.38mmol) and 3-vinylbenzaldehyde (0.289g, 2.19mmol) were added to a 500ml round flask and dissolved in 200ml of dichloromethane.

Then, a solution in which trifluoroacetic acid (20 ml, 0.26 mmol) was diluted in 200 ml of dichloromethane solvent was added thereto. The solution was left at room temperature for 12 hours without stirring.

After 12 hours, 40 ml of dichloromethane was added over 10 minutes with vigorous stirring of the solution. After that, a solution in which DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 1 g, 3.8 mmol) was dissolved in 60 ml of toluene was added over 10 minutes. After the addition, stirring was further performed for 15 minutes.

After completion of the reaction, the solvent was volatilized and passed through a silica gel to reduce the volume. At this time, the solution was filtered by passing the silica layer while flowing dichloromethane. The filtered solution was purified again by passing through a silica column. A dark green band was separated by flowing a solution of dichloromethane and hexane in a ratio of 1: 4, and the solvent was evaporated after collecting the band.

This material was once again purified by preparative thin layer chromatography (PTLC) to finally obtain H ₃ (3DT-10VC) corrol.

H ₃ (3DT-10VC) (49.52 mg; 2%). m / z (M ⁺ ): 564.144 (calc); 564.100 (obs). V _NH (KBr, cm ⁻¹ ): 3431.

λ _max (log ε / (M ⁻¹ cm ⁻¹ )): 653 (4.05); 621 (4.06); 577 (4.09); 421 (4.93) [soret band]; 292 (4.31).

<Example 2>

5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole; How to prepare [H ₃ (PFP-10VC)]

The method of preparing H ₃ (PFP-10VC) is the same as that of H ₃ (3DT-10VC) described above, except that 5 (pentafluorophenyl) dipyrromethane corresponds to the same mole number instead of 5 (3-thienyl) dipyrromethane. After purification using H ₃ (PFP-10VC) was obtained.

H ₃ (PFP-10VC) (150 mg, 6.4%). m / z (M ⁺⁺ 1): 733.137 (cal); 733.791 (obs). V _NH (KBr, cm ⁻¹ ); 3421.

¹ H NMR (CDCl ₃ ): 9.05 (d, J = 3.6 Hz, 2H); 8.75 (b, 4 H); 8.57 (b, 2 H); 8.24 (b, 1 H); 8.07 (d, J = 3.8 Hz, 1 H); 7.79 (d, J = 7.4 Hz, 1H); 7.71 (t, 1 H); 6.97 (dd, J ₁ = 10.8 Hz and J ₂ = 17.5 Hz, 1H); 5.95 (d, J = 17.7 Hz, 1 H); 5.40 (d, J = 10.9 Hz, 1H).

¹³ C NMR (CDCl ₃ ): 147.36 144.86 143.03 141.51 140.49 139.27 136.72 136.56 134.08 132.48 127.81 127.46 125.57 122.00 117.49; 114.76 114.03 113.16 31.59 29.71; 22.70 14.10.

λ _max (log ε / (M ⁻¹ cm ⁻¹ )): 638 (3.80); 612 (4.02); 561 (4.24); 411 (4.99) [soret band]; 297 (4.21).

<Example 3>

Iron (IV) 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole chloride; Method for preparing Fe (3DT-10VC) Cl

H ₃ (3DT-10VC) Cl (100 mg, 0.18 mmol) was dissolved in DMF (N, N-dimethylformamide, 50 ml) under a nitrogen atmosphere. Add about 4 times more FeCl ₂ . While the mixture was refluxed for about 1 hour, it was observed that the color of the mixture changed from green to reddish brown. After this, the temperature was lowered to cool the solution and the solvent was volatilized to obtain a solid precipitate.

This solid substance was dissolved in diethyl ether (OEt ₂ ) to obtain a [Fe (3DT-10VC) (OEt ₂ ) ₂ ] compound. Purification of this material through a silica flash column and volatilization of the solvent yields a pure reddish brown solid material. [Fe (3DT-10VC) (OEt ₂ ) ₂ ] is dissolved in dichloromethane and washed with 7% hydrochloric acid and water. In the process, the color of dichloromethane changes from reddish brown to dark brown. The material washed with water was dried over magnesium sulfate, and the solvent was volatilized using a vacuum dryer.

Finally, the Fe (3DT-10V) Cl compound was recrystallized from benzene and n-heptane solution to obtain pure material.

Fe (3DT-10VC) Cl (109.80 mg, 94.96%). m / z (M ⁺ Cl ⁻ ): 617.055 (calc); 617.042 (obs).

λ _max (log ε / (M ⁻¹ cm ⁻¹ )): 648 (3.53); 510 (4.16); 412 (4.71) [soret band]; 358 (4.63); 289 (4.37).

<Example 4>

Iron (IV) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole chloride; Method for preparing Fe (PFP-10VC) Cl

It is similar to the above-mentioned manufacturing process of Fe (3DT-10VC) Cl, but H ₃ (PFP-10VC) was used instead of H ₃ (3DT-10VC).

Fe (PFP-10VC) Cl (91.00 mg, 81.21%). m / z (M ⁺ Cl ⁻ ): 785.048 (calc); 785.219 (obs).

¹ H NMR (CDCl ₃ ):-1.22 (b, 2H; pyrrole-H); -2.79 (b, 2H; pyrrole-H); -15.93 (b, 2H; pyrrole-H); -37.17 (b, 2H; pyrrole-H).

λ _max (log ε / (M ⁻¹ cm ⁻¹ )): 622 (3.60); 505 (3.98); 394 (4.62) [soret band]; 366 (4.58).

Example 5

Copper (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole]; Manufacturing Method of Cu (PFP-10VC)

H ₃ (PFP-10VC) (50 mg, 0.068 mmol) was added to a 50 ml round bottom flask, and 10 ml of pyridine was dissolved. An excess of copper (II) acetate monohydrate was added to the solution, followed by stirring at room temperature for 30 minutes. You can see the color of the solution changes from purple to brown.

The solvent was volatilized under reduced pressure and the remaining material was dissolved in dichloromethane and purified through a silica column. Dichlroromethane and hexane were mixed in a 1: 1 ratio to obtain pure brown Cu (PFP-10VC).

Cu (PFP-10VC) (51 mg, 94.57%). m / z (M ⁺ +1): 793.053 (calc); 793.131 (obs).

¹ H NMR (CDCl ₃ ): 7.95 (d, J = 3.1 Hz, 2H, pyrrole-H); 7.57 (d, J = 2.3 Hz, 2H, pyrrole-H); 7.43 (d, J = 6.6 Hz, 2H, pyrrole-H); 7.39 (d, J = 4.0 Hz, pyrrole-H); 7.19 (b, 4 H); 6.76 (dd, J ₁ = 10.9 Hz and J ₂ = 17.9 Hz, 1H); 5.79 (d, J = 17.5 Hz, 1 H); 5.30 (d, J = 10.9 Hz, 1H).

<Example 6>

Cobalt (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole bispyridine; Manufacturing method of Co (PFP-10VC) · 2py

H ₃ (PFP-10VC) (50 mg, 0.068 mmol) was dissolved in 10 ml of hot pyridine solvent and refluxed for 1 hour by adding about 3 times excess Co (OAc) ₂ .4H ₂ O. At this time, the color changes from purple to green. After 1 hour the solution was cooled to room temperature and the solvent and volatiles were volatilized under reduced pressure.

The green material was dissolved in a small amount of dichloromethane solvent and filtered. Diethyl ether was added to the filtered solution to separate the brown precipitate. The filtered green material material was dissolved in dichlroromethane and the n-heptane solvent was slowly diffused to obtain recrystallization.

Co (PFP-10VC) .2py, 58 mg (90.1%). m / z (M ⁺ -2 Py): 788.047 (calc.); 788.111 (obs).

¹ H NMR (CDCl ₃ ): 9.07 (d, J = 3.7 Hz, 2H, pyrrole-H); 8.78 (b, 2 H, pyrrole-H); 8.66 (b, 2 H, pyrrole-H); 8.50 (b, 2 H, pyrrole-H); 8.07 (s, 1 H); 7.88 (d, J = 7.4 Hz, 1 H); 7.7 (d, J = 7.8 Hz, 1H); 7.57 (t, 1 H); 6.89 (dd, J ₁ = 10.9 Hz and J ₂ = 17.6 Hz, 1H); 6.20 (b, 2 H); 5.87 (d, J = 17.1 Hz, 1H); 5.27-5.33 (m, 5 H); 0.88 (t, 4 H).

<Example 7>

Manganese (III) 5,15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole; Manufacturing method of Mn (PFP-10VC)

Dissolve H ₃ (PFP-10VC) (50 mg, 0.068 mmol) in 15 ml of DMF solvent in a round bottom flask. Mn (OAc) ₂ · 4H ₂ O (50 mg, 0.20 mmol) was added thereto and heated for 20 minutes. After the reaction was completed, the reaction was cooled to room temperature and the solvent was evaporated with a reduced pressure dryer. The remaining material after solvent volatilization was purified through a silica column. At this time, the solution was pure Mn (PFP-10VC) using a 1: 1 solution of hexane and ethylacetate.

Mn (PFP-10VC) (50 mg, 93.73%). m / z (M ⁺ ): 794.052 (calc); 794.215 (obs).

<Example 8>

Catalytic reaction with Iron (IV) 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole chloride;

Styrene (2.99 mL, 26 mmol) and iodosylbenzene (0.572 g, 2.6 mmol) were dissolved in benzene (1 mL) under nitrogen atmosphere, and then Iron 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole chloride (unbound) (0.016 g, 0.026 mmol) was added.

The product was analyzed using nitrobenzene (0.22 mL, 2.6 mmol) as an internal reference and GC-MS. A small amount of sample was taken every hour with a syringe and a small silica column was passed through to remove impurities.

As a preliminary result, as shown in FIG. 1, styrene was first converted into styrene oxide, and secondary benzylaldehyde production was observed. White solid material has also been produced that has not yet been identified, which is thought to provide a clue that may explain the reduced concentration of styrene.

As described above, the vinyl-substituted metal-corrole material according to the present invention shows potential for novelty and catalytic application of the material. The metal-corrole compound prepared according to the present invention can achieve chemisorption with silica in which the surface is modified with a thiol group in which the vinyl group is substituted in the meso position, wherein the metal-corrol chemisorbed on the silica surface is a new non-uniform system. It can be used as a catalyst. In addition, it forms non-covalent bonds with thiol groups present in the structure of biomolecules such as nucleic acids (DNAzyme) and protein molecules. The substance is similar to the structure of heme, which constitutes hemoglobin, which has implications for the simulation of biomolecules and is expected to provide new uses in the fields of drug development and bioenzyme action.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated that it can be changed.

Claims (11)

Metal-Corol represented by the following general formula (1) is a vinyl-substituted metal-Corrol catalyst, characterized in that the metal is introduced in the center of the corrrole compound consisting of four pyrroles. [Formula 1]

The metal-coroll catalyst according to claim 1, wherein the corol compound has a thiophene or pentafluoro group in the 5th and 15th positions and is substituted with a vinyl group in the 10th carbon position. The metal-coroll catalyst according to claim 1, wherein the corol compound is substituted with one vinyl group at the meso position of the 10th carbon. The vinyl-substituted metal-corrole catalyst according to claim 1, wherein the metal is composed of a divalent metal or a trivalent metal. [Claim 2] The vinyl-substituted metal-corrole catalyst according to claim 1, wherein the divalent metal is iron, copper, zinc, or trivalent metal, and iron, manganese, cobalt, chromium, gallium, ruthenium, or indium. . The metal-coroll catalyst according to claim 1, wherein the vinyl group substituted at the 10th carbon site is a non-uniform catalyst which forms chemisorption with silica modified with thiol groups. The vinyl-substituted metal-corrole catalyst according to claim 1, wherein the vinyl group substituted at the 10th carbon site is bonded to a biomolecule. 2. The vinyl-substituted metal-coroll catalyst according to claim 1, wherein the metal-coroll catalyst is used for oxidation reactions such as epoxidation of olefins, hydroxylation of alkanes or propaneization of alkenes. Preparing a corrrole compound consisting of four pyrroles having a vinyl group (A), and introducing a metal into the center of the corrole compound to prepare a stabilized metal-corrole catalyst (B). Method for producing a metal-corrole catalyst substituted with a vinyl group. 10. The method of claim 9, wherein the corrrole compound is characterized in that 5,15-di (3-thienyl) -10- (3-vinylphenyl) corrole or 5, 15-di (pentafluorophenyl) -10- (3-vinylphenyl) corrole Method for producing a metal-corrole catalyst substituted with a vinyl group. The metal substituted with a vinyl group according to claim 9, wherein the metal is any one selected from iron, copper, zinc, trivalent metal, iron, manganese, cobalt, chromium, gallium, ruthenium, and indium. Process for preparing corol catalyst.

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