WO2019146961A1 - 산성 화합물 검출용 조성물 - Google Patents
산성 화합물 검출용 조성물 Download PDFInfo
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- WO2019146961A1 WO2019146961A1 PCT/KR2019/000714 KR2019000714W WO2019146961A1 WO 2019146961 A1 WO2019146961 A1 WO 2019146961A1 KR 2019000714 W KR2019000714 W KR 2019000714W WO 2019146961 A1 WO2019146961 A1 WO 2019146961A1
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- C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/28—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups acylated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/70—Metal complexes of oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
Definitions
- the present application claims the benefit of priority based on Korean Patent Application No. 10 2018-0010273, filed on January 26, 2018, the entire contents of which are incorporated herein by reference.
- the present invention relates to a composition for detecting an acidic compound and a method for detecting an acidic compound using the same.
- the hybrid material formed by the formation of the network composed of the organic-metal composite can overcome the limitations of the organic material wood material made of a single material, and can realize the respective advantages by simultaneously realizing the respective properties.
- the structural diversity of the material and the sophistication of the design can be maximized.
- Representative industrial applications of such organo-metal complexes include energy storage, bio-medicine, sensors, semiconductor circuit devices, and the like.
- metal logels have recently begun to be studied in earnest. Metallogels are produced by a mechanism in which solvent is trapped in the intermaterial space in the course of the formation of a polymer or network of metal ions and mul t identate ligands.
- Structural diversity which is the advantage of the organo-metal complexes mentioned above, can be realized through the coordination of various ligands and various metal ions. It also has the advantage of using a small amount of gel-forming gelator to make large volume bulk materials and to control the physical properties.
- Metal-gel which is an organic-metal composite material, can detect gas molecules using changes in coordination structure, unlike organogel. For example, the pH change induced by acidic gas molecules can be detected with a metal gel. When the pH of the solvent inside the acidic gas molecular gel is changed, the metal dissociates and the network collapses, As a result, a physical change (sol-gel transition) occurs in which the bulk material changes into a solution phase and collapses. This allows the detection of acidic gas molecules.
- a sensing strategy that uses oxidation-reduction reactions that change the oxidation number of metals to gas molecules is actively studied (T. Pal et al., ACS Appl. Mater. Interfaces 2014, 6308-6316).
- the present inventors confirmed the reactivity of the metal-gel complex, which is an organo-metal complex, to exhibit visually easily visible sol-gel transition by reacting with an acidic compound. Based on this, the metallogels were synthesized by varying the composition and weight percent of the various metal-ligand combinations.
- the present inventors have completed the present invention by confirming that the sensitivity can be controlled according to the type and weight percentage of the metal through measurement of the time during which various kinds of gels change into a liquid phase through the solgal transition under an acidic gas flow.
- the present invention provides a composition for detecting an acidic compound and a method for detecting an acidic compound using the same.
- the present invention provides a composition for detecting an acidic compound, which comprises an organometallic complex formed by coordination bonding of a compound represented by the following general formula (1) or a salt thereof and a metal ion:
- Each of the seedlings is independently selected from the group consisting of - 3 ⁇ 4, - (-) - 3 ⁇ 4,
- 3 ⁇ 4 is alkyl containing 1-10 0 0 6-60 aryl, or £ 0 and any one of
- the compound represented by the above formula (1) has a biphenyl (group) parent structure and is capable of charge transfer through a pie-conjugation.
- the compound represented by the formula (1) has a hydroxy group in each benzene ring and has two imines at the ortho ( 0 ) position of the hydroxy group. Through the hydroxy group and the imine group, Combination is possible.
- the compound represented by the above-mentioned general formula (1) is a compound in which a substituent group substituted in an imine group is a substituent group capable of further coordinate bonding with a metal ion, Or an amine group (-? -?).
- the coordination bond with the metal ion through the hydroxyl group and the imine group it is possible to further coordinate bond with the metal ion, so that the compound represented by the formula 1 and the metal ion form a two-dimensional or three-dimensional network structure .
- the hydroxy group of the phenoxide, the imine group and the oxime moiety can coordinate bond with various metals.
- a coordination network can be formed in the form of a gel (for), and the expected network structure is shown in FIG.
- the organometallic complex is a metal gel, which is characterized by being reacted with an acid compound to be converted into a liquid, which can be visually confirmed and used for the detection of an acidic compound.
- a deprotonated ligand under basic conditions forms a network and is present as a metal gel, it reacts with an acidic compound to dissociate metal ions through protonation of the ligand, Collapsed and converted into a liquid phase.
- Metal of the metal ion is not particularly proposed, for example, V,! 3 ⁇ 4, 0 0,, 0 11, 1 containing a 3 ⁇ 4 period transition metals, 2! ,] 3 ⁇ 4, grave 11 , 13 ⁇ 4 1 ,? 1, Shouyou, etc., as well as a lanthanide metal such as 3 ⁇ 4, Yb and Yb as well as a three-period transition metal such as a transition metal, a ratio, and Au.
- each R is independently selected from - (3 ⁇ 4, phenyl, naphthyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert- butyl, pentyl, tert- pentyl, neopentyl, Pentyl, 3-pentyl, or alanine, cysteine, aspartic acid, glutamic acid, phenylalanine, histidine, isoleucine, lysine, leucine, methionine, asparagine, pyrrolizine, glutamine, arginine, serine, threonine, selenocysteine, , Tyrosine, etc.
- amino acid residue refers to a structure in which an amino group is excluded from the structure of an amino acid.
- the amine group condenses with an aldehyde to form an imine.
- the group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert- pentyl, neopentyl, isopentyl, Naphthyl, or pyridinyl. 2019/146961 1 (: 1 ⁇ ⁇ 2019/000714
- the compound represented by Formula 1 When the compound represented by Formula 1 includes a carboxyl group, it may exist in the form of a salt, This can be + .
- Representative examples of the compound represented by the formula (1) are any of the compounds represented by the following formulas (1-1) to (1-5)
- the present invention also provides a process for preparing a compound represented by the formula (1)
- the method comprises the steps of: (1) preparing a compound represented by Formula 3 'by reacting a compound represented by Formula I, a compound represented by Formula 2', and trifluoroacetic acid; And reacting the compound represented by Formula 3 with the compound represented by Formula 4 '.
- the above step 1 is a Duf f reaction, 2019/146961 1 (: 1 ⁇ ⁇ 2019/000714
- the reaction temperature in step 1 is 10010 to 1501 :.
- the reaction time of step 1 is 1 day to 10 days. After the reaction of Step 1, a step of obtaining a product may be added.
- reaction mixture may be added to an excess of 1 to 5 molar hydrochloric acid and stirred for one to three days to obtain a precipitate.
- the precipitate may be recrystallized from dimethylsulfoxide to obtain the compound represented by formula (3 ').
- Step 2 is a reaction in which aldehyde and hydroxyamine react to form aldooxime, which is a reaction in which aldooxime is formed in the aldehyde of the compound represented by Formula 3 '.
- the seedlings are as defined defined above in formula (I).
- the solvent of the reaction of Step 2 is preferably water, 0 1-4 alcohol, or a mixed solvent thereof, more preferably a water / ethanol mixed solvent or a water / methanol mixed solvent .
- a step of obtaining a product may be added.
- an excess amount of water is added to the resultant precipitate, which is then filtered and washed with water and acetone in order to obtain the compound represented by Formula 2019/146961 1 (: 1 ⁇ ⁇ 2019/000714
- the organometallic complex may be prepared by mixing the compound represented by the formula (1) and the precursor of the metal.
- the molar ratio of the compound represented by Formula 1 to the metal precursor is 1: 1 to 1: 4, preferably 1: 2 (when a metal having a coordination number of 6 is used) or 1: 3 4 metal is used).
- the solvent is preferably dimethylsulfoxide or dimethylformamide, and more preferably at least one equivalent of a base such as triethylamine or sodumethoxide is used.
- the reaction is from 10 to 401. Further, after the above reaction, ultrasonic treatment or heating at 1001: to 140 ⁇ (: for 10 minutes to 10 hours can be added.
- the organometallic complex according to the present invention is characterized in that it is converted into a liquid by reacting with an acidic compound, and this process can be visually confirmed and used for the detection of an acidic compound.
- the acidic compound means a compound which induces the transition of the organometallic complex according to the present invention.
- the acidic compound is in the form of a liquid or gas, more preferably in the form of a gas.
- Specific examples of the acidic compound include hydrogen chloride, hydrogen fluoride, hydrogen bromide, trifluoroacetic acid, acetic acid, and nitrogen oxides, 3 ⁇ 4), nitric acid, sulfuric acid ratio 3 ⁇ 4), or sulfuric acid.
- the organometallic complex according to the present invention was changed to a liquid phase upon exposure to hydrogen chloride gas, and it was confirmed that there was a difference in the rate of change to liquid depending on the weight percentage and type of metal ion.
- 2019/146961 1 (: 1 ⁇ ⁇ 2019/000714
- composition for detecting an acidic compound according to the present invention is characterized in that the detection of an acidic compound can be confirmed visually by using the characteristics of the organometallic complex.
- Fig. 1 schematically shows the network structure of the organometallic complex of the present invention.
- Fig. 2 shows a state in which the composition for detecting an acidic compound of the present invention is mounted in a cylinder.
- Fig. 3 is a graph showing the time (seconds) required for the organometallic complex of the present invention to change to liquid.
- FIG. 4 shows the cobalt-metal gel in the experiment of the present invention changing into liquid with time by weight percentage.
- FIG. 5 is a graph showing the change of the copper metal hydrogel in terms of weight per unit weight with time in the experimental example of the present invention.
- FIG. 6 is a graph showing the change of the zinc metal gel to a liquid in 20 hours by weight per weight in the experimental example of the present invention.
- FIG. 7 shows the results of the time course of the dissolution of zinc metal gel by trifluoroacetic acid in the experimental example of the present invention.
- HMTA hexamethylenetetramine, 7.530 g, 53.70 mmol
- TFA trichloroacetic acid 50 mL
- biphenyl-4,4'_diol 1.000 g, 5.370 mmol
- the product was dark red, which was poured into 4N HCK 100 mL) and the yellow precipitate was filtered.
- the precipitate was recrystallized with hot DMSO to obtain 2.460 g (yield: 65.1%) of yellow fine crystals.
- the compound (tetraoxime biphenol, 25 3 ⁇ 4 ) prepared in the above Production Example was dissolved in 3 ⁇ 40.88), followed by dropwise addition of triethylamine (0.02 ⁇ ) Solution A was prepared.
- the solution A (0.1 mL) and the solution B (0.4 mL) were mixed to prepare a metallogel, which was then sonicated for 1 minute to increase the strength of the metallogel.
- the metallogel thus prepared was named "Cobalt metallogel 2 wtV.
- a solution 8 was prepared by dissolving 3 ⁇ 4 ( 3 % ( 2 ) 0 0 (50 1 ⁇ ) in 0 (4.15 mol). The solution was mixed with the solution (0.1) and the solution 6 (0.4) to prepare a metal gel, which was then sonicated for 1 minute to increase the strength of the metal gel.
- the metal gel thus prepared 111 1 (3 ⁇ 4 6 1 2 3 ⁇ 4 / ').
- Solution Show 8 and Solution 8 were prepared in the same manner as in Example 3-1 except that 0 pseudo-dose was adjusted as shown in Table 3 below. [Table 3]
- a certain volume of the inside of the cylinder The metal gel was put in. After the o-ring was attached and the system was isolated from the outside by using a clamp, hydrogen chloride gas was flowed into the cylinder at a constant flow rate and flow rate. Then, the time (second) was measured while observing the melted state of the metal gel. The time required for complete melting of the metal gel is shown in Table 4, and the images observed at a certain time interval with the graph (FIG. 3) are shown in FIGS.
- Zinc metal logel (1.2 mL) of 4 wt% prepared in Example 3-2 was placed inside the cylinder.
- An o-ring was fitted to one end of the cylinder and connected to an oil bubbler to check the internal pressure of the cylinder.
- the other end of the cylinder was connected to a round bottom flask containing trifluoroacetic acid and a Tigon tube. Nitrogen was poured into a round bottom flask to allow the trifluoroacetic acid vapor to pass through the cylinder and the melting process of the metal gel was recorded as a digital image and captured at a constant time interval (20 seconds) .
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Abstract
본 발명에 따른 산성 화합물 검출용 조성물은 유기금속 복합체의 특성을 이용하여 시각적으로 산성 화합물의 검출을 확인할 수 있다는 특징이 있다.
Description
【발명의 명칭】
산성 화합물검줄용조성물
【기술분야】
관련출원 (들)과의 상호인용
본 출원은 2018년 1월 26일자 한국 특허 출원 제 10 2018-0010273호에 기초한우선권의 이익을주장하며, 해당한국특허 출원의 문헌에 개시된모든 내용은본명세서의 일부로서 포함된다. 본발명은산성 화합물검출용조성물및 이를사용하여 산성 화합물을 검출하는방법에 관한것이다.
【배경기술】
유기-금속 복합체로 구성된 네트워크의 형성으로 만들어진 하이브리드 물질은, 단일소재로이루어진유기 재료나무기 재료가갖는한계를뛰어넘어 각자의 장점을 동시에 구현하여 새로운 물성을 가질 수 있다. 또한, 유기 성분과 무기 성분의 선택 및 조합을 통해 물질의 구조적 다양성과 디자인의 정교함도 극대화할 수 있다. 이러한유기-금속 복합체의 대표적 산업적 이용 사례로, 에너지 저장, 생체의약품, 센서, 반도체회로소자등이 있다. 유기-금속 복합체 중에서 메탈로젤 (metal logel)은 최근에 본격적으로 연구되기 시작했다. 메탈로젤은 다자배위성 (mul t identate) 리간드와 금속 이온이 중합체 또는 네트워크를 형성하는 과정에서 물질 간 공간에 용매가 포집되는 메커니즘을통해 생성된다. 구조적으로 다양한 리간드와 여러 금속 이온의 배위 결합을 통해 앞서 언급한 유기-금속 복합체의 장점인 구조적 다양성을구현할수 있다. 또한, 소량의 젤형성 분자 (gelator)를이용해서 큰 부피의 벌크물질을만들고물성을제어할수있다는장점도있다. 유기-금속 복합 재료인 메탈로젤은 유기젤 (organogel )과 달리 배위 결합구조의 변화를 이용하여 기체 분자를 감지할수 있다. 예를들어, 산성 기체 분자에 의해 유발되는 pH변화를 메탈로젤로감지할수 있다. 산성 기체 분자가젤내부용매의 pH를변화시키면금속이 해리되어 네트워크가붕괴되고,
그결과벌크물질이 용액 상으로 변화하여 무너져 내리는물리적 변화 (졸-겔 전이; sol -gel transi t ion)가생긴다. 이를통해 산성 기체 분자를감지할수 있다. 이외에도, 기체 분자가 금속에 배위하여 금속의 산화수를 변화시키는 산화-환원반응을이용하는감지 전략도활발히 연구되었다 (T. Pal et al. ACS Appl . Mater. Interfaces 2014, 多, 6308-6316) . 본발명자들은유기-금속복합체인 메탈로젤이 산성 화합물에 감응하여 시각적으로쉽게 확인 가능한졸-겔전이를보이는반응성을확인하였다. 이를 토대로, 다양한 금속-리간드 조합의 조성과 중량 퍼센트 (weight percent)를 바꾸며 메탈로젤을합성하였다. 산성 기체 흐름하에서 여러 종류의 젤이 졸 갤 전이를 통하여 액체 상으로 변하는 시간의 측정을 통해, 금속의 종류와 중량 퍼센트에 따라 감응성을 제어할 수 있음을 확인하여 본 발명을 완성하였다.
【발명의 내용】
【해결하려는과제】
본발명은산성 화합물검출용조성물및 이를사용하여 산성 화합물을 검출하는방법을제공하기 위한것이다.
【과제의 해결수단】
상기 과제를 해결하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물또는 이의 염과금속 이온의 배위 결합으로형성된 유기금속복합체를 포함하는, 산성 화합물검출용조성물을제공한다:
[화학식 1]
상기 화학식 1에서,
은 각각 독립적으로, -0比 06-60 아릴, 01-10 알킬, 또는 아미노산 잔기이고,
¾는 01-10 알킬, 06-60아릴, 또는 0및 £중 어느하나를포함하는
04-60헤테로아릴이다 . 상기 화학식 1로 표시되는 화합물은 비페닐( 기)의 모핵 구조를 가지고 있으며, 파이-컨쥬게이션(끄-이미 ))을 통하여 전하 이동( 묘 : 군라)이 가능하다. 또한, 상기 화학식 1로 표시되는 화합물은 각 벤젠 고리에 하아드록시기를가지고 있으며, 하이드록시기의 오르쏘(0 如) 위치에 2개의 이민기를 가지고 있으며, 이러한 하이드록시기와 이민기를 통하여 금속과배위 결합이 가능하다. 특히, 상기 화학식 1로 표시되는 화합물은, 하이드록시기 및 이민기 외에, 이민기에 치환되어 있는치환기 묘가금속 이온과추가적인 배위 결합이 가능한 ¾ 치환기, 아미드
또는 아민기(- !€-¾)룰 가질 수 있다는 특징이 있다. 이에 따라 상기 하이드록시기 및 이민기를 통한 금속 이온과의 배위 결합 외에도, 추가적으로 금속 이온과 배위 결합이 가능하여, 상기 화학식 1로표시되는화합물과금속이온은 2차원또는 3차원의 네트워크 구조가형성된다. 일례로, 상기 화학식 1에서 요이 -에인 화합물은 페녹사이드와 이민기 및 옥심 부분의 하이드록시기가여러 금속과배위 결합을할수 있다. 염기성 조건에서 이 화합물에 금속 염을 첨가할 경우 젤(용 )의 형태로 배위 결합 네트워크를형성할수있으며, 예상되는네트워크의 구조는도 1에 나타내었다. 상기 유기금속복합체는메탈로젤로서, 산상화합물과반응하여 액체로 변환되는특징이 있으며, 이 과정은시각적으로확인 가능하여 산성 화합물의 검출에사용할수있다.
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구체적으로, 상기 유기금속복합체는염기성 조건하에서 탈양성자화된 리간드가금속과배위하여 네트워크가형성되어 메탈로젤로존재하므로, 산성 화합물과 반응하여 리간드의 양성자화를 통해 금속 이온이 해리되면서 네트워크가붕괴되어 액체상으로변환된다. 상기 금속 이온의 금속은특별히 제안되지 않으며, 일례로 , V, !¾, 00 , , 011 , ¾을포함하는 1주기 전이금속, 2! , ]¾ , 묘11, 1¾1 , ? 1, 쇼요등 2주기 전이금속, 比, 라, Au등 3주기 전이금속뿐만 아니라, ¾, 묘 Yb등 란탄족 금속도 포함한다. 특히, 산성 화합물을 검출한다는 점에서, 어, , 또는 ¾이 바람직하다. 상기 화학식 1에서, 바람직하게는, ¾이 -抑, 또는아미노산잔기이다. 바람직하게는, 은각각독립적으로, -(¾, 페닐, 나프틸, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 터트-부틸, 펜틸, 터트-펜틸, 네오펜틸, 이소펜틸, 드 -펜틸, 3 -펜틸, 또는알라닌, 시스테인, 아스파르트산, 글루탐산, 페닐알라닌, 히스티딘, 아이소류신, 라이신, 류신, 메티오닌, 아스파라긴, 피롤라이신, 글루타민, 아르기닌, 세린, 트레오닌, 셀레노시스테인, 발린, 트립토판, 타이로신으로 구성되는 군으로부터 선택되는 어느 하나의 아미노산의 잔기이다. 상기에서 아미노산 잔기란, 아미노산의 구조에서 아민기를 제외한 구조를 의미한다. 아민기는 알데하이드와축합하여 이민을 형성한다. 예컨대, 알라닌
경우, 알라닌의 구조에서 아민기를 제외한 프로판산 (! ¾)1011 % 1)이 아미노산잔기가된다. 또한 바람직하게는, ¾는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 터트-부틸, 펜틸, 터트-펜틸, 네오펜틸, 이소펜틸, -펜틸, 3- 펜틸, 핵실, 옥틸, 페닐, 나프틸, 또는피리디닐이다.
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또한, 상기 화학식 1로 표시되는 화합물이 카르복시기를 포함하는 경우에는염의 형태로존재할수있으며, 이때
이)은 +, 될수있다. 상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기 화학식 1-1 내지 1_5로표시되는화합물중어느하나이다:
[화학식 1-1]
、! 014
[화학식 1-3]
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[반응식 1]
구체적으로, 상기 제조 방법은, 상기 화학식 I로 표시되는 화합물, 상기 화학식 2'로표시되는화합물및트리플루오로아세트산을반응시켜, 상기 화학식 3’로표시되는화합물을제조하는단계 (단계 1) ; 및 상기 화학식 3로 표시되는 화합물을 상기 화학식 4’로 표시되는 화합물과 반응시키는 단계를 포함한다. 상기 단계 1은, Duf f 반응 (Duf f react ion)으로서, 상기 화학식 1’로
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표시되는 화합물의 하이드록시기의 오르쏘 (01^110) 위치에 알데하이드기를 치환시키는반응이다. 바람직하게는, 상기 화학식 1로 표시되는 화합물과 상기 화학식 2로 표시되는 화합물의 몰비는 1:20이다. 또한, 상기 트리플루오로아세트산은 용매의 역할도동시에 하는것으로, 상기 화학식 1로표시되는화합물과상기 화학식 2로 표시되는 화합물을모두용해시킬 수 있을 정도로사용하는 것이 바람직하다. 바람직하게는, 상기 단계 1의 반응온도는 10010 내지 1501:이다. 또한 바람직하게는, 상기 단계 1의 반응시간은 1일내지 10일이다. 상기 단계 1의 반응 후, 생성물을 수득하는 단계가 추가될 수 있다. 일례로, 1몰내지 5몰의 과량의 염산에 반응혼합물을첨가하고, 1일내지 3일 동안 교반하여 침전물을 얻을 수 있다. 이의 정제를 위하여, 침전물을 다이메틸설폭사이드로 재결정하여 화학식 3’로 표시되는 화합물을 얻을 수 있다. 상기 단계 2는, 알데하이드와 하이드록시아민이 반응하여 알도옥심을 형성하는 반응으로서, 상기 화학식 3’로 표시되는 화합물의 알데하이드에 알도옥심을형성시키는반응이다. 상기 화학식 41로표시되는화합물에서,묘와 정의는앞서 화학식 1에서 정의한바와같다. 상기 단계 2의 반응의 용매로는 물, 01-4 알코올, 또는 이들의 혼합 용매가 바람직하며, 물/에탄올혼합용매, 또는 물/메탄올 혼합용매가보다 바람직하다. 상기 단계 2의 반응 후, 생성물을 수득하는 단계가 추가될 수 있다. 일례로, 상기 단계 2의 반응 후, 과량의 물을 첨가하여 생성되는 침전물을 여과하고, 물과 아세톤으로 차례로 세척하여 화학식 1로 표시되는 화합물을
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얻을수있다. 또한, 상기 유기금속복합체는, 상술한화학식 1로표시되는화합물및 상기 금속의 전구체를혼합하여 제조할수있다. 바람직하게는, 상기 화학식 1로 표기되는 화합물과 금속 전구체의 몰 비는 1 : 1내지 1 :4이고, 바람직하게는 1 : 2(배위수가 6인 금속을사용할경우) 또는 1 : 3(배위수가 4인 금속을 사용할 경우)이다. 또한, 용매는 디메틸설폭사이드 혹은 디메틸포름아마이드가 바람직하며, 추가로 트라이에틸아민이나소둠 메톡사이드 등의 염기를 1당량 이상사용하는 것이 바람직하다. 바람직하게는, 상기 반응은 10내지 401:이다. 또한, 상기 반응이후에, 초음파 처리, 또는 1001: 내지 140°(:에서 10분 내지 10시간 동안 가열이 추가될수있다. 상술한 바와 같이, 본 발명에 따른 유기금속 복합체는 메탈로젤로서, 산성 화합물과 반응하여 액체로 변환되는 특징이 있으며, 이 과정은 시각적으로확인가능하여산성 화합물의 검출에사용할수있다. 상기 산성 화합물은 본 발명에 따른 유기금속 복합체의 전이를 유도하는 화합물을 의미한다. 바람직하게는, 상기 산성 화합물은 액체 또는 기체의 형태이며, 보다 바람직하게는 기체의 형태이다. 또한, 상기 산성 화합물의 구체적인 예로는 염화수소, 불화수소, 브롬화수소, 트리플루오로아세트산, 아세트산, 질소산화물어¾), 질산, 황산화물比¾), 또는황산을들수있다. 후술할 실시예와 같이, 본 발명에 따른 유기금속 복합체는 염화수소 기체에 노출시 액체상으로 변화하였으며, 중량 퍼센트와금속 이온의 종류에 따라 액체로 변하는 속도의 차이가 있음을 확인할 수 있었다. 이를 통하여,
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산성 화합물가스 센서로의 응용가능성을확인하였을뿐만아니라, 유기금속 복합체의 조성을 제어함으로써 가스 센서의 감도를 향상시킬 수 있음을 확인하였다.
【발명의 효과】
5 상술한 바와 같이, 본 발명에 따른 산성 화합물 검출용 조성물은 유기금속복합체의 특성을 이용하여 시각적으로산성 화합물의 검출을확인할 수있다는특징이 있다.
【도면의 간단한설명】
도 1은, 본 발명의 유기금속 복합체의 네트워크의 구조를 모식적으로 10 나타낸것이다.
도 2는, 본 발명의 산성 화합물 검출용 조성물이 실린더 내 장착된 모습을나타낸것이다.
도 3은, 본 발명의 유기금속 복합체가 액체로 변화하는데 소요된 시간(초)을그래프로나타낸것이다.
15 도 4는, 본 발명의 실험예에서 코발트 메탈로젤이 중량 퍼센트 별로 시간에 따라액체로변화하는모습을나타낸것이다.
도 5는, 본 발명의 실험예에서 구리 메탈로젤이 중량 퍼센트 별로 시간에 따라액체로변화하는모습을나타낸것이다.
도 6는, 본 발명의 실험예에서 아연 메탈로젤이 중량 퍼센트 별로 20 시간에 따라액체로변화하는모습을나타낸것이다.
도 7은, 본 발명의 실험예에서 아연 메탈로젤이 트리플루오로아세트산에 의하여 녹아 내리는 과정을 시간별로 나타낸 결과를 나타낸것이다.
【발명을실시하기 위한구체적인내용】
25 이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나하기의 실시예는본발명을보다쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해본발명의 내용이 한정되는것은아니다. 제조예 : 테트라옥심비페닐다이올의 제조
(단계 1)
건조된 둥근 바닥플라스크에 HMTA(hexamethylenetetramine, 7.530 g, 53.70 mmol)을 넣었다. 상기 플라스크를 아르곤으로 퍼징하고, TFA tr i f luoroacet i c acid, 50 mL)를 넣었다. HMTA를 완전히 용해시킨 후, 비페닐- 4,4’_디올(1.000 g, 5.370 mmol)을 빠르게 넣었다. 상기 혼합물이 오렌지색이 된 것을 확인한 후, 120°C로 7일 동안 가열하였다. 생성물은 검붉은색이었으며, 이를 4N HCK100 mL)에 부어 노란색 침전물을 여과하였다. 침전물을 뜨거운 DMS0로 재결정하여 노란색의 미세결정 2.460 g(수율: 65.1%)을얻었다.
(단계 2)
가열하였다. 상기 혼합물이 투명해질 때까지 메탄올을 적가하였다. 반응기를 단단히 밀봉한후 100°(:로 1시간동안 가열하였다. 상온으로 냉각한후 물을 첨가하여 침전물을 유도하고, 이를 여과 및 물로 세척하여 밝은 노란색의 생성물 이쌔아, 0.360은)을얻었다.
¾■ (300 mz, ■쌨대) 5 11.60 (£ , 4 , 10.88 ( ¾) , 8.45 (£ , , 7.83 , £) 실시예 1-1내지 1-4
1)실시예 1-1
앞서 제조예에서 제조한 화합물(테트라옥심바이페놀, 25 ¾)을 ¾0 0.88 0 )에 녹이고, 이어 트라이에틸아민(0.02 此)을 적가하여 혼합한
용액 A를 준비하였다. 또한, CO(0AC)2 · 4¾0(35 mg)을 DMF(3.53 mL)에 녹인 용액 B를준비하였다. 상기 용액 A(0.1 mL)와상기 용액 B(0.4 mL)를혼합하여 메탈로젤을 제조한 후, 1분 동안 초음파 처리하여 메탈로젤의 강도를 증가시켰다. 이렇게 제조한 메탈로젤을 "Cobalt metallogel 2 wtV로 명명하였다.
2)실시예 1-2내지 1-4
용액 A및용액 B의 제조시 하기 표 1과같이 DMF의 사용량을조절하는 것을제외하고는, 상기 실시예 1-1과동일한방법으로메탈로젤을제 하였다. 【표 1]
1)실시예 2-1
앞서 제조예에서 제조한 화합물 (테트라옥심바이페놀, 25 !雄)을 ■(1.09 此)에 녹이고, 이어 트라이에틸아민 (0.02 )을 적가하여 혼합한 용액 쇼를 준비하였다. 또한, ^(3030)2(55 1雄)을 0^(4.36 1此)에 녹인 용액 8를 준비하였다. 상기 용액 사0.1 1 )와 상기 용액 6(0.4 1 )를 혼합하여 메탈로젤을 제조한 후, 1분 동안 초음파 처리하여 메탈로젤의 강도를 증가시켰다. 이렇게 제조한 메탈로젤을 "(¾不 111 31 10용61 2 % "로 명명하였다.
2)실시예 2-2내지 2-4
1)실시예 3-1
앞서 제조예에서 제조한 화합물(테트라옥심바이페놀, 25 >眼)을
■(1.04 此)에 녹이고, 이어 트라이에틸아민(0.02 此)을 적가하여 혼합한 용액 요를 준비하였다. 또한, ¾(%3(:)2 · ¾0(50 1收)을 0 (4.15 此)에 녹인 용액 8를준비하였다. 상기 용액쇼(0.1 )와상기 용액 6(0.4 )를혼합하여 메탈로젤을 제조한 후, 1분 동안 초음파 처리하여 메탈로젤의 강도를 증가시켰다. 이렇게 제조한메탈로젤을
111 1(¾61 2 ¾/’로명명하였다.
2)실시예 3-2내지 3-4
용액쇼및용액 8의 제조시 하기 표 3과같이 0 의사용량을조절하는 것을제외하고는, 상기 실시예 3-1과동일한방법으로메탈로젤을제조하였다. 【표 3]
도 2과 같이, 실린더 내부에 일정 부피의 앞서 제조한 실시예의
메탈로젤을넣었다. 오-링을장착하고클램프를이용하여 시스템을외부로부터 격리시킨 후, 일정한 유속과 유량으로 염화 수소 가스를 실린더 내부로 흘려보냈다. 이후 메탈로젤이 녹아 내리는 모습을 관찰하면서 시간(초)을 측정하였다. 메탈로젤이 완전히 녹아내리는데 소요되는 시간을 하기 표 4에 나타내었고, 이를그래프(도 3)와일정 시간간격에 따라관찰한이미지를도 4내지 6에 나타내었다.
【표 4]
상기와 같이, 짧은 시간 내에 염화수소 가스를 검출할 수 있었으며, 메탈로젤의 금속 및 중량%에 따라 시간 차이를 나타냄을 확인할 수 있었다. 따라서, 상기와 같은 특성을 이용하여 산성 화합물의 검출 및 이의 감도를 제어할수있음을확인할수있다. 실험예 2
도 2와 같이, 실린더 내부에 실시예 3-2에서 제조한 4 wt%의 Zinc metal logel (1.2 mL)를넣었다. 실린더의 한쪽끝에 오-링을장착하고, 실린더 내부 압력 확인을 위해 오일 버블러와 연결하였다. 실린더의 다른쪽끝에는 트리플루오로아세트산이 들어있는 둥근 바닥 플라스크와 타이곤 튜브로 연결하였다. 둥근바닥플라스크에 질소를흘려 보내서, 트리플루오로아세트산 증기가 실린더를 통과하게 하며, 메탈로젤이 녹아 내리는 과정을 디지털 영상으로 녹화하고, 이를 일정 시간 간격 (20 초)마다 캡쳐하여 도 7로 나타내었다.
Claims
[화학식 1]
¾은 각각 독립적으로, _(犯, Ce-eo 아릴, 01-10 알킬, 또는 아미노산 잔기이고
¾는 01-10 알킬, 06-60아릴, 또는 0및 중 어느하나를포함하는 04-60헤테로아릴이다.
【청구항 2]
제 1항에 있어서,
¾은 각각 독립적으로, ~0\{ , 페닐, 나프틸, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 터트-부틸, 펜틸, 터트-펜틸, 네오펜틸, 이소펜틸, -펜틸, 3 -펜틸, 또는알라닌, 시스테인, 아스파르트산, 글루탐산, 페닐알라닌, 히스티딘, 아이소류신, 라이신, 류신, 메티오닌, 아스파라긴, 피롤라이신, 글루타민, 아르기닌, 세린, 트레오닌, 셀레노시스테인, 발린, 트립토판, 타이로신으로 구성되는 군으로부터 선택되는 어느 하나의 아미노산의 잔기인것을특징으로하는,
산성 화합물검출용조성물.
2019/146961 1»(:1^1{2019/000714
【청구항 3】
제 1항에 있어서,
¾는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 터트-부틸, 펜틸, 터트-펜틸, 네오펜틸, 이소펜틸,
3 -펜틸, 핵실, 옥틸, 페닐, 나프틸, 또는피리디닐인 것을특징으로하는,
산성 화합물검출용조성물.
【청구항 4]
제 1항에 있어서,
상기 화학식 1로 표시되는 화합물은, 하기 화학식 1-1 내지 1-5로 표시되는화합물인것을특징으로하는,
산성화합물검줄용조성물:
[화학식 1-1]
[화학식 1-2]
\ 02019/146961 1»(:1^1{2019/000714
[화학식 1-4]
2019/146961 1»(:1^1{2019/000714
【청구항 5]
제 1항에 있어서,
상기 금속 이온의 금속은, 1주기 전이금속, 2주기 전이금속, 3주기 전이금속, 또는란탄족금속인 것을특징으로하는,
2019/146961 1»(:1^1{2019/000714
산성 화합물검출용조성물.
【청구항 6]
제 1항에 있어서,
산성 화합물검출용조성물.
【청구항 7】
제 1항에 있어서,
상기산성 화합물은액체또는기체인,
산성 화합물검줄용조성물.
【청구항 8]
제 1항에 있어서,
상기 산성 화합물은 염화수소, 불화수소, 브롬화수소, 트리플루오로아세트산, 아세트산, 질소산화물, 질산, 황산화물, 또는황산인, 산성 화합물검출용조성물.
【도면】
【도 1】
【도 2]
1/6
RECTIFIED SHEET (RULE 91) ISA/KR
Weight precent (wt%)
2/6
3/6
RECTIFIED SHEET (RULE 91) ISA/KR
[Si 5]
4/6
5/6
6/6
RECTIFIED SHEET (RULE 91) ISA/KR
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