KR20090079491A - Synthesis and anion recognition of calix[6]arene bridged bipyridine methal-complex of noble optical ionophores - Google Patents

Abstract

A method for manufacturing an anion recognition receptor of calixarene is provided to selectively produce a receptor of color and fluorescence anion in solution using a calyx[6]arene as a host. A method for manufacturing a calix[6]arene compound of the chemical formula 1 which bipyridine is connected comprises a step of reacting amino calyx[6]arene compound of the chemical formula 4 with acyl halide compound of the chemical formula 5. In the chemical formula 1 or 4, R is hydrogen or alkyl group of C1-C7. In the chemical formula 5, X is selected from Cl or Br. A method for manufacturing ruthenium calyx[6]arene compound of the chemical formula 2 compound comprises: a step of reacting the calyx[6]arene compound with ruthenium of the chemical formula 7 to obtain ruthenium calyx[6]arene chloride; and a step of reacting ruthenium calyx[6]arene chloride with ammonium hexafluorophosphate(NH4PF6) to obtain the ruthenium calixs[6]arene compound of the chemical formula 2.

Description

Synthesis and anion recognition of calix [6] arene bridged bipyridine methal-complex of noble optical ionophores}

The present invention relates to a method for producing anion recognition receptor of the calix arene system and a sensor for detecting anion including the anion recognition receptor prepared therefrom.

Living organisms are a collection of large molecules such as DNA, RNA, and proteins from metal ions or small organic molecules, and the most fundamental of the phenomena of life is the mutual recognition between these members. It is a natural activity. Molecular recognition is characterized by the relationship between host and guest, and research is being conducted on compounds called supramolecular molecules. Hypermolecular chemistry has become widely known by Jean-Marie Lehn, and supramolecular molecules for use as hosts can recognize other molecules or ions that are not covalently linked by relatively weak forces, such as hydrogen bonds or dipole bonds. Suramolecular Chemistry of Anions (Eds: Bianchi, A .; Bowman James, K .; Garcia-Espana, E.), WILEY-VCH, New York, 1997.

Currently known anion receptors of the Calixarene family are mostly Kalix [4] arene derivatives, which were developed by several researchers including the Beer, PD group and the inventors of Korea (Matthews, SD; Beer, PD Supramol. Chem). 2005, 17, 411.). Calix [6] Aren (Gutsche, CD; Bauer, LJJ Am, Chem. Soc. 1985, 107, 6052.), Calix [4] Aren (Gutsche, CD; Dhawan, B .; Levine, JA; No, Compared to KH; Bauer, LJJ Am, Chem. Soc. 1983, 39, 409.), its size is large and its structure is diverse.

As described above, it is necessary to develop a color and fluorescent anion receptor that selectively recognizes anions in solution by using a less developed calix [6] aren as a host among the callix arenes which are actively used for supramolecular research. .

The present invention provides to the host a Kalix [6] arene that can enhance the recognition ability of the host molecule and the anion, and the luminescence or fluorescent signal through the ruthenium or rhenium complex before and after the anion recognition Its purpose is to provide identifiable chromogenic receptors.

The inventors of the present inventors conducted a study to produce a fluorescent and anionic receptor that selectively recognizes anions in solution using a calix [6] arene as a host, and thus the lower rim of the calix [6] arene structure. ) Was prepared a calix [6] arene compound having an amide group (-NHCO-) and connecting bipyridine, the rupynium group or rhenium-based bipyridine group of the calix [6] arene compound Anion recognition receptors have been prepared by binding compounds.

Therefore, the present invention is a bipyridine-linked calyx [6] arene compound and a method for preparing the same, ruthenium calix [6] arene compound represented by the formula (2) and a method for preparing the same, and Provided are a rhenium calix [6] arene compound and a method of preparing the same.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3, R is selected from hydrogen or an alkyl group of C1 to C7.)

Hereinafter, a method for producing a calex [6] arene compound according to the present invention will be described in detail.

Method for producing a bipyridine-linked calyx [6] arene compound represented by the formula (1) according to the present invention is the reaction of the amino calyx [6] arene compound of the formula (4) and the acyl halide compound of A step of preparing a Kalix [6] arene compound of 1 is included.

[Formula 1]

[Formula 4]

[Formula 5]

In Formula 1 or Formula 4, R is selected from hydrogen or an alkyl group of C1-C7, more specifically R is hydrogen or methyl, and R is methyl. In Formula 5, X is selected from Cl or Br, and X is more preferably Cl.

The acyl halide compound of Chemical Formula 5 is more preferably acyl chloride prepared by reacting a dicarboxylic acid compound of Chemical Formula 6 with thionyl chloride (SOCl ₂ ) in a methylene chloride solvent.

[Formula 6]

In addition, the method for preparing the Kalix [6] Arene compound of Chemical Formula 1 is to purify the Kalix [6] Arene compound of Chemical Formula 1 by a column chromatography method after preparing the Calix [6] Arene compound of Chemical Formula 1; The method may further include a step, wherein it is preferable to use a mixed solvent of methylene chloride and methanol as an eluant.

An example of the method for preparing the compound of Formula 1 according to the present invention is shown in Scheme 1. The compound of Formula 4 may be prepared through a known method (Kim, DS; Yang, YS; Nam, KC Bull. Korean Chem. Soc . 1998. 19. 1133.).

Scheme 1

The present invention provides a method for preparing a ruthenium complex and rhenium complex from the compound of Formula 1.

The method for producing a ruthenium complex according to the present invention includes the following steps.

a) preparing a ruthenium calix [6] arene chloride by reacting the bipyridine-linked calix [6] arene compound of Formula 1 with a ruthenium compound of Formula 7; And

b) reacting the ruthenium calyx [6] arene chloride with ammonium hexafluorophosphate (NH ₄ PF ₆ ) to prepare a ruthenium calix [6] arene compound of formula (2).

[Formula 2]

[Formula 7]

The step a) is performed under a mixed solvent of alcohol and water and an acid catalyst, and the step b) is preferably performed in a mixed solvent of water and alcohol. Examples of the alcohol include methanol or ethanol, and acetic acid may be used as the acid catalyst.

In addition, the method for preparing a rhenium composite according to the present invention is a rhenium compound [6] arene of Formula 3, wherein a bipyridine-linked calix [6] arene compound and a rhenium compound of Formula 8 are reacted under an organic solvent. Preparing a compound. It is preferable to use ethers, such as tetrahydrofuran and diethyl ether, as said organic solvent.

[Formula 3]

[Formula 8]

Re (CO) ₅ Cl

In Formula 2 or Formula 3, R is selected from hydrogen or an alkyl group of C1 to C7, more preferably hydrogen or methyl, even more preferably methyl.

In another aspect, the present invention provides a sensor for detecting anions using the characteristics of the Kalix [6] arene metal complex of the formula (2) or (3) exhibits selective binding force to the anion and changes in color and fluorescence before and after bonding.

Recognition of molecules in host-guest chemistry takes advantage of non-covalent binding forces through various designs depending on the size, shape and charge of the guest molecule. Non-covalent bonds include relatively weak forces such as hydrogen bonds, dipole bonds, and electrostatic attraction (Comprehensive Supramolecular Chemistry, vol 1 and vol 2, Molecular Recognition, Pergamon, 1996.). The anion acceptor of Formula 2 and Formula 3 according to the present invention utilizes the electrostatic attraction and hydrogen bonding between N-H and the anion between two amides connected to the lower rim of Calix [6] arene.

In order for the host material to be used as a chemical sensor, the receptor must be able to convert the accompanying supramolecular phenomena into useful signals by recognizing or reacting negative ions. Examples of the converted signal include the formation of an electric field, a change in current flow, and a change in optical characteristics. There are two methods of using optical change: colorimetric sensors and luminescent sensors. The detection limit of the color sensor due to light absorption is a measure is possible in less than the limit (10 ^-6 mole / L) of an absorption coefficient, fluorescence was very weak even if the light is amplified by the detector Excellent 10 ^-9 mole / L or less (A) Bell TW; Hext NM, Chem. Soc. Rev. 2004, 33, 589-598. (B) Kang, SO; Powell, D .; Day, VW Bowman-James, K. Angewandte Chemie, Int. Ed. 2006, 45, 1921-1925. (C) Egorov, VV; Nazarov, VA; Okaev, EB; Pavlova, TEJ Anal.Chem. 2006, 61, 382- 388. (d) Chung, YM; Raman, B .; Kim, D .; Ahn, KH Chem. Commun. 2006, 186-188. (E) Fillaut, J .; Andries, J .; Toupet, L .; Desvergne, J. Chem. Commun. 2005, 2924-2926.).

 The anion receptors of formulas (2) and (3) according to the present invention employ ruthenium and rhenium complexes at the extreme ends of the host material for the optical signal by complex formation between various anion guest analytes and the host receptor. Provide change. Particularly, in the present invention, the Calix [6] arene metal complexes of Formulas 2 and 3 show a significantly higher binding force to carboxylic acid anions such as acetic acid anion or benzoic acid anion, and thus are more suitable for use in sensors for detecting carboxylic acid anions. Suitable.

As described above, the present invention provides a method of connecting ruthenium complex and rhenium complex to supramolecular molecules, and thus will be applied to the preparation of chromogenic metal complex ligands of many supramolecular compounds studied at home and abroad. Since the Kalix [6] arene compound has a high binding force to aliphatic or aromatic carboxylic acid anions, many applications may be possible as sensors for identifying carboxylic acid anions in a liquid phase.

Hereinafter, the present invention will be described in detail by way of examples, but the following examples are merely examples of the present invention, and the scope of the present invention is not limited by the following examples.

Example 1

5, 11, 17, 23, 29, 35-hexa-tertiary-butyl-37, 40-bis (aminoethoxy) -38, 39, 41, 42-tetramethoxycalix linked to bipyridine [6] Preparation of arene (Formula 1)

Dissolve compound (R = methyl) (1.1 g, 1.0 mmol) of formula 4 in 100 mL of purified chloroform under nitrogen and mix triethylamine (0.5 mL, 3.6 mmol) in 300 mL of purified methylene chloride. After adding biscarboxyl bipyridine compound of formula 6 (0.32 g, 1.3 mmol) and SOCl ₂ (20 mL, 0.27 mol) to 100 mL of methylene chloride, the mixture was refluxed for 3 days and mixed slowly with bipyridine acyl chloride for 5 hours. After reflux it was refluxed for 12 hours. After confirming that the reaction was completed by TLC, the organic solvent was removed by distillation under reduced pressure. The solid remaining after distillation under reduced pressure was subjected to column chromatography using methylene chloride: methanol (10: 1) as a developing solvent to obtain 38% (0.5 g) of a pale pink solid (IV).

¹ H NMR (CD ₂ Cl ₂ ) δ 8.69 (d, 2H, BpH, J = 4.8 Hz), 8.09 (s, 2H, BpH), 7.87 (broad s, 2H, NH), 7.63 (d, 2H, BpH , J = 4.9 Hz), 7.07, 6.98 and 6.62 (three s, 12H, ArH), 4.35, 3.68, 3.38 and 3.24 (two pair of d, 12H, ArCH ₂ Ar), 4.07 and 3.94 (two t, 8H, -OCH ₂ CH _2- ), 2.81 (s, 12H, -OCH ₃ ), 1.16 and 1.04 (two s, 54H, -C (CH ₃ ) ₃ ). ¹³ C NMR (CD ₂ Cl ₂ ) δ 167.38 (-CONH-), 157.17, 153.99, 152.35, 150.84, 146.79, 146.14, 144.18, 133.78, 126.15, 126.02, 121.72 and 120.06 (Bp and Ar), 71.75 (-OCH _2- ), 60.58 (-OCH ₃ ), 41.45 (-CH ₂ N-), 34.42, 34.27, 31.46, 31.42 and 30.44 (ArCH ₂ Ar and -C (CH ₃ )).

MAS-FAB m / z: 1346 [M ⁺ Na] ⁺ . Anal. Calcd for C ₈₆ H ₁₀₆ N ₄ O ₈ : C, 78.06; H, 8.02; N, 4.24. Found: C, 74.93; H, 8.85; N, 3.92.

Example 2

5, 11, 17, 23, 29, 35-hexa-tertiary-butyl-37, 40-bis (aminoethoxy) -38, 39, 41, 42-tetramethoxycalix linked to bipyridine ruthenium complex [6] Arene Production Formula 2

5, 11, 17, 23, 29, 35-hexa-tertiary-butyl-37, 40-bis (aminoethoxy) -38, 39, 41, 42-tetra with bipyridine linked to 35 mL of purified ethanol Dissolve methoxycalix [6] arene (Formula 1) (0.4 g, 0.27 mmol), add 5 mL distilled water and 1 mL acetic acid, and then add [RuCl ₂ (bipy) ₂ ] .2H ₂ O. During reflux. After confirming that the reaction was completed by TLC, the organic solvent was removed by distillation under reduced pressure. The solid remaining after distillation under reduced pressure was subjected to column chromatography using a developing solvent of methanol: acetic acid (8: 1) to obtain a solid compound. And NH ₄ PF ₆ and the obtained compound is dissolved in distilled water: methanol (50: 40 mL) and stirred for 1 hour. 50 mL of methylene chloride is added thereto, mixed well, and the organic layer is separated. The separated organic layer is distilled off under reduced pressure to obtain a remaining solid. This solid was dried in vacuo for 2 days to yield 50% (0.3 g) of an orange solid.

¹ H NMR (CD ₃ CN) δ 9.00 (s, 2H, BpH), 8.49 (dd, 4H, BpH), 8.08 (m, 4H, BpH), 8.04 (s, 2H, -CONH), 7.84 (dd, 4H, BpH), 7.64 (d, 2H, BpH), 7.48 (d, 2H, BpH), 7.42 (t, 2H, BpH), 7.25 (t, 2H, BpH), 7.1-6.7 (six s, 12H, ArH), 4.5-3.1 (three pair of d, 12H, ArCH ₂ Ar), 4.1-3.7 (m, 8H, -OCH ₂ CH ₂ N-), 3.07-2.76 (two s, 12H, -OCH ₃ ), 1.09, 1.05 and 1.03 (three s , 54H, -C (CH 3) 3. 13 C NMR (CD 3 CN) δ 164.18 (-CO-), 157.64, 157.29, 157.13, 153.99, 152.65, 152.05, 151.49, 146.44 , 146.00, 154.94, 143.47, 138.57 , 138.46, 133.77, 133.47, 133.21, 133.17, 133.03, 132.90, 128.25, 128.13, 126.23, 125.98, 125.82, 124.84, 124.79 and 122.80 (Bp and Ar), 71.12 (-OCH 2 - ), 60.29 (-OCH ₃ ), 41.53 (-CH ₂ N-), 34.47, 34.19, 31.15, 29.61, 29.33 and 29.22 (ArCH ₂ Ar and -C (CH ₃ )). MAS-FAB m / z: 1882 [M-PF ₆ ] +. Anal.Calcd for C ₁₀₆ H ₂₁₂ N ₈ O ₈ RuF ₁₂ 5H ₂ O; C, 60.14; H, 6.24; N, 5.29.Found: C, 60.18; H, 6.46; N, 5.09.

Example 3

5, 11, 17, 23, 29, 35-hexa-tertiary-butyl-37, 40-bis (aminoethoxy) -38, 39, 41, 42-tetramethoxycalix linked to bipyridine rhenium complex [ 6] Production of arene (Formula 3)

5, 11, 17, 23, 29, 35-hexa-tertiary-butyl-37, 40-bis (aminoethoxy) -38, 39, 41 with bipyridine linked to 5 mL of purified tetrahydrofuran under nitrogen , 42-tetramethoxycalix [6] arene (Formula 1) (0.13 g, 0.1 mmol) was dissolved, Re (CO) ₅ Cl (0.036 g, 0.1 mmol) was added, and the mixture was refluxed for 5 hours. After confirming that the reaction was completed by TLC, the organic solvent was removed by distillation under reduced pressure. The solid remaining after the distillation under reduced pressure was subjected to column chromatography using a developing solvent of methylene chloride: methanol (50: 1) to obtain a yellow solid compound (70%, 0.1 g).

¹ H NMR (CDCl ₃ ) δ 8.81 (d, 4H, BpH), 8.54 (s, 2H, BpH), 7.97 (d, 4H, BpH), 6.97 (s, 2H, -CONH), 7.02-6.59 (three s, 12H, ArH), 4.37-3.6 (three pair of d, 12H, ArCH ₂ Ar), 3.05-3.5 (m, 8H, -OCH ₂ CH ₂ N-), 2.97 (two s, 12H, -OCH ₃ ), 1.09, 1.1 and 0.88 (three s, 54H, -C (CH ₃ ) ₃ ).

Experimental Example 1 Anions Binding Characteristics of Calix [6] Arene Ruthenium Complex of Chemical Formula 2

The binding force between the ions and the host is found by obtaining the stability constant ( K _a ). The stability constant can be expressed in the following way. When complexes are formed between compounds, they are briefly described as follows. Where H represents a host or a receptor and G represents a guest.

Here, the complex formation-dissociation constant k ₊ / k _- is called the stability constant ( K _a ). In this experiment, the stability constant was determined by spectroscopic ¹ H NMR titration experiment to reveal the degree of intermolecular attraction between the anion guest and the ion receptor, formula (2).

^{In 1} H NMR titration, the receptor is dissolved in a certain NMR solvent to a specific concentration, and then titrated with an anionic solution of known concentration. Stability constant is determined by using EQ-NMR through chemical movement of the binding site according to the binding between receptor and anion.

Determination of stability constants using EQ-NMR is known from the following disclosure. (Michael JH J. Chem . Soc ., Dalton Trans . 1993 , 311.)

¹ H NMR titration experiment was carried out using DMSO- d ₆ as NMR solvent. Alternatively, as a host, CH ₃ COO ⁻ , PhCO ₂ ⁻ , H ₂ PO ₄ ⁻ , Cl ⁻ , PhCH ₂ CO ⁻ , and NfCO ₂ ⁻ anions were used as hosts as the host of Formula 2 synthesized in Example 2 to CD ₃ CN. Each anion used tetrabutylammonium salt. As a result of NMR experiments, the chemical shift of the hydrogen peak of NH, an amide moiety, in the structure of Chemical Formula 2 was observed, and each anion could be regarded as binding between two amides.

[Table 1] Stability constant ( K _a ) between the compound of Formula 2 and the anions

Experimental Example 2 Anions Binding Properties of Calix [6] arerenium Complex of Formula 3

¹ H NMR titration experiments the formula (3) prepared in Example 3 in DMSO- d ₆ as a solvent by NMR host _{^{CH 3 COO -, PhCO 2 -}} , H 2 PO 4 -, Cl -, Br -, I - anions Was used as a guest. Each anion used tetrabutylammonium salt. As a result of NMR experiments, the chemical shift of the hydrogen peak of NH, an amide moiety, in the structure of Formula 3 is observed, and each anion may be regarded as binding between two amides.

Table 2 The stability constants (Ka) with the compound with the anion of formula (3)

Claims (10)

A bipyridine represented by the following Chemical Formula 1, comprising the step of reacting an amino-calix [6] arene compound of Formula 4 with an acyl halide compound of Formula 5 to prepare a Calix [6] arene compound of Formula 1 Method for producing the linked calix [6] arene compound. [Formula 1]

[Formula 4]

[Formula 5]

(In Formula 1 or Formula 4, R is selected from hydrogen or an alkyl group of C1 ~ C7, and in Formula 5, X is selected from Cl or Br.) The method of claim 1, R is methyl and X is Cl, wherein the bipyridine represented by the formula (1) is linked to the calyx [6] arene. The method of claim 2, The acyl halide compound represented by Chemical Formula 5 may be an acyl chloride prepared by reacting a dicarboxylic acid compound represented by Chemical Formula 6 with thionyl chloride (SOCl ₂ ) in a methylene chloride solvent. Process for preparing linked calix [6] arene compound. [Formula 6]

The method of claim 1, After the step of preparing the Kalix [6] arene compound of Formula 1 further comprising the step of purifying the Kalix [6] arene compound of Formula 1 by a column chromatography method using a mixed solvent of methylene chloride and methanol, A method for producing a bilixin-linked calyx [6] arene compound represented by 1. a) preparing ruthenium calyx [6] arene chloride by reacting the bipyridine-linked calyx [6] arene compound of Formula 1 prepared from the method of claim 1 with a ruthenium compound of Formula 7; And b) reacting the ruthenium calix [6] arene chloride with ammonium hexafluorophosphate (NH ₄ PF ₆ ) to prepare a ruthenium calix [6] arene compound of Chemical Formula 2; Method for producing a ruthenium callix [6] arene compound of the formula (2) comprising a. [Formula 1]

[Formula 2]

[Formula 7]

(In Formula 1 or Formula 2, R is selected from hydrogen or an alkyl group of C1 to C7.) The method of claim 5, wherein The a) step is a method for producing a ruthenium calix [6] arene compound of the formula (2), characterized in that carried out under a mixed solvent of alcohol and water and an acid catalyst. A rhenium compound [6] arene of Formula 3 is prepared by reacting a calyx [6] arene compound having a bipyridine linked to the bipyridine of Formula 1 and a rhenium compound of Formula 8 under an organic solvent. Method of preparing a rhenium calyx [6] arene compound of the formula (3) comprising the step. [Formula 1]

[Formula 3]

[Formula 8] Re (CO) ₅ Cl (In Formula 1 or Formula 3, R is selected from hydrogen or an alkyl group of C1 to C7.) The method of claim 7, wherein The organic solvent is a method for producing a rhenium calix [6] arene compound of formula 3, characterized in that selected from ethers. A sensor for detecting carboxylic acid anion, comprising a calix [6] arene compound prepared from claim 5 or 7. The method of claim 9, The carboxylic acid anion is an anion detection sensor, characterized in that the acetic acid anion or benzoic acid anion.