KR20170080865A

KR20170080865A - Composition for detecting trichlorocyanuric acid and detecting method of trichlorocyanuric acid using the same

Info

Publication number: KR20170080865A
Application number: KR1020150190267A
Authority: KR
Inventors: 장석규; 이슬기
Original assignee: 중앙대학교 산학협력단
Priority date: 2015-12-30
Filing date: 2015-12-30
Publication date: 2017-07-11

Abstract

The present invention relates to a composition for detecting trichlorosanooic acid, which is a chloramine, and a method for detecting trichlorosanooic acid using the composition for detecting trichlorosanooic acid.

Description

TECHNICAL FIELD The present invention relates to a composition for detecting trichlorosuccinic acid and a method for detecting trichlorosuccinic acid using the same,

The present invention relates to a composition for detecting trichlorosanooic acid, which is chloramine, and a method for detecting trichlorosanooic acid using the composition for detecting trichlorosanooic acid.

Chloramine is an inorganic or organic nitrogen compound comprising one or more chlorine atoms attached to a nitrogen atom. The chloramine is an environmentally friendly oxidant that is inexpensive, stable in aqueous solution, and widely used for everyday life and industrial applications. Since chloramines are easier to handle than chlorine gas or metal hypochlorite, they are widely used as drinking water purification and sanitary treatment of swimming pools. In addition, the chloramines are generally used in synthetic reactions. The availability of chloramine results from the fact that it reacts as a source of halide ions and various nitrogen-containing compounds. As a result, these reagents can react with a wide range of functional groups leading to many molecular conversions such as chlorination of alkenes and aromatics, oxidation of ether and alcohol groups, epoxidation of alkenes, and nitrosation of amine groups. In organic synthesis, hypochlorite can also be replaced by N-chloramine, especially when anhydrous conditions are required. Among the organic chloramines, especially trichloroisocyanuanic acid (TCCA) and sodium N-chloro-p-toluenesulfonamide (chloramine-T) are becoming increasingly important.

In general, chloramines have been analyzed by titrimetry, amperometry, and flow-injection analysis using iodides. Detailed analytical methods such as HPLC, GC, and mass spectrometry have also been used. The colorimetric method using N, N-diethyl-p-phenylenediamine (DPD) is a commonly used technique for analyzing chlorine in water. However, we have not found any literature using fluorescence signaling for chloramine analysis.

Reaction-based probes have attracted much attention recently due to the special and cumulative signaling advantages. In particular, the reaction-based probes have a noticeable effect on the signaling or visualization of oxygen or nitrogen compounds such as hydrogen peroxide, nitric acid nitrate, and hypochlorous acid which have a biologically important reaction. However, optical probes for practical oxidants such as peracid and chloramine have rarely been reported despite the importance of various industrial applications [(a) Eor, S.; Choi, M. G .; Kim, N .; Sun, T .; Chang, S.-K. Tetrahedron Lett. 2012, 53, 4080; (b) Eor, S.; Hwang, J .; Choi, M. G .; Chang, S.-K. Org. Lett. 2011, 13, 370; (c) Cha, S .; Hwang, J .; Choi, M. G .; Chang, S.-K. Tetrahedron Lett. 2010, 51, 6663; (d) Choi, M. G .; Cha, S .; Park, J. E .; Lee, H .; Jeon, H. L .; Chang, S.-K. Org. Lett. 2010, 12, 1468.].

The present invention provides a composition for detecting trichlorosuccinic acid, which is chloramine, and a method for detecting trichlorosyanooic acid using the composition for detecting trichlorosanooic acid.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

A first aspect of the present invention provides a composition for detecting trichlorosyanooic acid comprising a coumarin oxime compound represented by Formula 1:

[Chemical Formula 1]

In Formula 1, R ₁ is optionally substituted alkyl groups of linear or branched C _1-6, C _1-6 alkoxy group which may be substituted, which may be an alkynyl group, or a substituted C _2-7 C _6-12 aryl group.

A second aspect of the present invention provides a method for detecting trichlorosanooic acid using a fluorescent signal of a composition for detecting trichlorosyanooic acid according to the first aspect of the present application.

In one embodiment of the present invention, by using a fluorescence signal generated by trichlorosyanooic acid, which is a chloramine, generated when an oxime derivative of coumarin oxime is oxidized and converted into a carbonyl group, an eco- A method for detecting trichlorosuccinic acid can be provided.

The composition for detecting trichlorosyanooic acid according to one embodiment of the present invention is capable of selectively emitting a selective fluorescence signal to the trichlorosyanooic acid irrespective of the kinds of metal ions or anions such as alkali metals, alkaline earth metals, , And the reaction for the detection is stable in a wide range of about pH 3 to about pH 10.

1 is a fluorescence spectrum of coumarin oxime according to the kind of oxidizing agent in one embodiment of the present invention.
2 shows the fluorescence intensity ratio of coumarin oxime according to the kind of the oxidizing agent in one embodiment of the present invention.
FIG. 3 is a UV-vis spectrum of coumarin oxime according to the kind of the oxidizing agent in one embodiment of the present invention. FIG.
Figure 4 is a partial ¹ H NMR spectrum of coumarin oxime and 7-ethoxy coumarin, with and without TCCA, in one embodiment of the invention.
Figure 5 is a partial ¹³ C NMR spectrum of coumarin oxime and 7-ethoxy coumarin, with and without TCCA, in one embodiment of the invention.
Figure 6 shows the fluorescence intensity ratio of coumarin oxime with and without TCCA in the presence of metal ions in one embodiment of the invention.
Figure 7 shows the fluorescence intensity ratio of coumarin oxime with and without TCCA in the presence of anions in one embodiment of the invention.
Figure 8 shows the fluorescence intensity ratio of coumarin oxime with and without TCCA in the presence of metal ions in one embodiment of the invention.
9 shows the fluorescence intensity ratio of coumarin oxime with and without TCCA in the presence of an anion in one embodiment of the present invention.
Figure 10 shows the effect of pH on the fluorescence intensity of a coumarin oxime-TCCA system in one embodiment of the invention.
11 shows the change in fluorescence intensity of coumarin oxime containing coumarin oxime and TCCA over time in one embodiment of the present invention.
Figure 12 shows the fluorescence intensity of coumarin oxime according to the concentration of TCCA in one embodiment of the invention.
Figures 13 (a) and 13 (b) are images of fluorescence intensity and blue channel intensity, respectively, according to the concentration of TCCA under UV lamp, in one embodiment of the invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Throughout this specification, the term "chloramine" means a compound in which hydrogen (H) of ammonia (NH ₃ ) is replaced with chlorine (Cl), which is used as a disinfectant for waterworks. : 3 in water at the same time, chloramine (NH ₂ Cl, NHCl ₂ ) is produced, and it exhibits a sterilizing effect while liberating hypochlorous acid (HClO) slowly. Throughout this specification, chloramine may be, but is not limited to, trichlorosyanooic acid, which is a chloramine.

Throughout this specification, the term "alkyl group" typically refers to a straight or branched alkyl group having from one to six carbon atoms. When the alkyl group is substituted with an alkyl group, it is used interchangeably with a "branched alkyl group ". Examples of substituents include halo (for example, F, Cl, Br, I), haloalkyl (e.g., CC1 ₃ or CF ₃ ), alkoxy, alkylthio, hydroxy, carboxy (-COOH) carbonyl (-C (O) R), alkylcarbonyloxy (-OCOR), amino (-NH _2), carbamoyl (-NHCOOR- or -OCONHR-), urea (-NHCONHR-) or thiol (-SH ), But the present invention is not limited thereto. In addition, the defined alkyl groups may include, but are not limited to, one or more carbon to carbon double bonds or one or more carbon to carbon triple bonds. But is not limited to, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, or all possible isomers thereof.

Throughout the specification, the term "alkynyl group" refers to an unsaturated straight-chain or branched hydrocarbon radical having usually 2 to 7 carbon atoms and 1 or 2 triple bonds at any position, for example, ethynyl, (2-propyn-1-yl), 1-propyne-1-yl, 1-yl, 1-penten-1-yl, 3-penten-1-yl, And the like, but the present invention is not limited thereto.

Throughout this specification, the term "alkoxy group" refers to an alkyl group as defined above wherein the alkyl group is linked to an oxygen atom, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, But may be, but not limited to, all isomers.

Throughout this specification, the term "aryl" refers to monocyclic, such as, for example, phenyl, substituted phenyl, and the like, as well as monocyclic, such as fused bicyclic, such as naphthyl, phenanthrenyl, Refers to a click aromatic ring. Wherein the aryl group contains at least one ring having at least 6 atoms and up to 5 of the rings contain up to 22 atoms and wherein the double bonds between adjacent carbon atoms or suitable heteroatoms are alternating Resonance). The aryl group may be substituted with at least one substituent selected from the group consisting of halogen, alkyl, alkoxy, hydroxy, carboxy, carbamoyl, alkyloxycarbonyl, nitro, trifluoromethyl, amino, cycloalkyl, cyano, alkylS (O) 2), or thiol. The term " alkyl " For example, the C _6-50 aryl group which is substituted or unsubstituted throughout the specification may be a benzene ring, a toluene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentaren ring, an indene ring, a biphenylene ring, A heterocyclic ring, an acenaphthylene ring, an acenaphthylene ring, an acenaphthylene ring, a fluorene ring, a tetracene ring, a triphenylene ring, a pyrene ring, a chrysene ring, an ethyl- A heterocyclic ring, a pentachene ring, a tetraphenylene ring, a hexaphen ring, a hexasene ring, a rubisene ring, a coronene ring, a trinaphthylene ring, a heptaphene ring, a heptacene ring, a pyranthrene ring, A phenanthryl group, a 1-pyrenyl group, a chrysenyl group, a naphthacenylene group, a coronyl group, and a cyclopentadienyl group; And derivatives thereof. However, the present invention is not limited thereto. There can not be.

Throughout this specification, the term "oxime" refers to a compound in which the aldehyde, the carbonyl group of the ketone, C═O is changed to C═NOH. For example, an oxime derived from an aldehyde is referred to as an alkoxide, and a oxime derived from a ketone is referred to as a ketoxime.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

[Chemical Formula 1]

In one embodiment of the present invention, the composition for detecting trichlorosyanooic acid may further include, but is not limited to, a metal ion or an anion. The composition for the detection of trichlorosyanooic acid may exhibit selective signaling to the trichlorosanooic acid in the presence of the metal ion or the anion, and is not limited to the kind of the metal ion or the anion .

In one embodiment of the invention, the metal ion is selected from the group consisting of Li, Na, K, Mg, Ca, Ba, Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Hg, Pb, And may include, but is not limited to, ions of a metal selected from the group consisting of

In one embodiment of the invention, the anion is selected from the group consisting of F ^- , Cl ^- , Br ^- , I ^- , HPO ₄ ² ^- , P ₂ O ₇ ⁴ ^- , SO ₄ ^2- , SO ₃ ^2- , NO ₃ ^- , HCO _But are not limited to, anions selected from the group consisting of ₃ ^- , OAc ^- , ClO ₄ ^- , S ^2- , and combinations thereof.

A second aspect of the present invention provides a method for detecting trichlorosanooic acid using a fluorescent signal of a composition for detecting trichlorosyanooic acid according to the first aspect of the present application. Although the detailed description of the parts overlapping with the first aspect of the present application is omitted, the description of the first aspect of the present invention can be applied equally to the second aspect.

In one embodiment of the invention, the trichlorosyanooic acid detection method utilizes the fluorescence signal of trichlorosyanooic acid generated as the oxime derivative of coumarin oxime undergoes oxidation conversion to a carbonyl group, The trichlorosyanooic acid, which is an environmentally friendly oxidizing agent used, may be detected but may not be limited thereto.

In one embodiment of the present invention, the oxime of the coumarin oxime may be converted to a carbonyl group to detect the trichlorosyanooic acid, but the present invention is not limited thereto.

In one embodiment of the present invention, the trichlorosyanooic acid detection method may be performed at about pH 3 to about pH 10, but may not be limited thereto. The fluorescence of the trichlorosyanooic acid may not be affected by changes in pH, but may not be limited thereto.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto.

[ Example ]

<Materials and Equipment>

7-ethoxycoumarin, hydroxylamine hydrochloride, Lawesson's reagent, and trichloroisocyanuric acid (TCCA) were purchased from Aldrich Chemical Co. All other chemicals and solvents were obtained from commercial sources and used as generally accepted. ¹ H NMR (600 NHz) and ¹³ C NMR (150 MHz) spectra were measured on a Varian VNS spectrometer and the residual solvent signal was referenced.

The UV-vis spectrum was recorded using a Jasco V-550 spectrophotometer equipped with a Peltier temperature controller. Fluorescence spectra were measured using a PTI QuantaMaster steady state fluorescence spectrometer. Mass spectra were obtained on a Micromass Autospec mass spectrometer. Fluorescence measurements were performed using spectrometer grade acetonitrile from Aldrich Chemical Co. Column chromatography was performed with silica gel (240 mesh).

<7- Of ethoxythio coumarin Manufacturing>

The Lewesson reagent (0.44 g, 1.1 mmol) was added to a solution of 7-ethoxycoumarin (0.19 g, 1.0 mmol) in toluene (15 mL). The mixture was refluxed for 12 hours and cooled at room temperature. The organic solvent was removed under reduced pressure. The residue was filtered using column chromatography (silica gel 240 mesh, 1 st eluent: dichloromethane, 2 nd eluent: ethyl acetate-hexane = 3: 1, v / v) to obtain thiocoumarin (0.13 g, 65%).

<7- Ethoxy coumarin - Oxime Manufacturing>

The 7-ethoxycomarine-oxime was prepared according to a modified procedure of the reported method for the preparation of spirodihydropyranochromen-2-one. Hydroxylamine hydrochloride (0.14 g, 2.0 mmol) and sodium acetate (0.16 g, 2.0 mmol) were added to a solution of 7-ethoxythiocoumarin (0.20 g, 1.0 mmol) in methanol (10 mL). The mixture was refluxed for 12 hours and cooled at room temperature. The organic solvent was removed under reduced pressure. The residue was filtered (0.16 g, 80%) using column chromatography (silica gel 240 mesh, eluent: dichloromethane-methanol = 9: 1, v / v) to yield coumarin-oxime.

<Characteristic Analysis>

A coumarin oxime probe for trichlorosyanooic acid signaling was prepared by a two-step reaction from 7-ethoxy coumarin. The 7-ethoxycoumarin containing Lawesson's reagent was thionated to give the tiocoumarin (toluene, 65%). Hydroxylamine and thiocoumarin were reacted to prepare 7-ethoxycoumarin oxime (NH ₂ OH, EtOH, 80%). In this example, attempts have been made to prepare coumarin derivatives of chromogenic more chromic acids with dialkylamino (coumarin 334) or benzothiazole substituents (coumarin 6). However, the stability of the dye source under the oxidative stress of the trichlorosyanooic acid under consideration in the present application was insufficient.

The coumarin oxime probe showed an absorption band at 325 nm (? _Max = 323 nm) on a 90% aqueous acetonitrile solution with phosphate buffer at pH 8.0, which is similar to 7-ethoxy coumarin. On the other hand, coumarin oxime probe showed weak fluorescence due to fluorescence quenching of the oxime group under the same conditions. In this example, the preliminary fluorescence signal of a coumarin oxime probe toward a series of substantial oxidants such as hydrogen peroxide, tert-butyl hydroperoxide (TBHP), perborate, peracetic acid (PAA), and chloramine TCCA (Figure 1 and Figure 2). Of the oxidants tested, only TCCA and hypochlorous acid (HOCl) showed noticeable signals under the measurement conditions. The increase of the fluorescence observed in the 392 nm I / I ₀ is 102 times the 105 times the TCCA and HOCl. Such colorimetric or fluorescent signaling of HOCl has been previously reported due to deoximation of oxime derivatives of various substances (such as BODIPY and phenanthroididazole dyes) in the carbonyl group of the HOCl. In addition, peroxide acetate showed a significant response _{(I / I 0 = 11.8)} . Other commonly used oxidizers such as hydrogen peroxide, TBHP, perborates, percarbonates, and peroxides show negligible signaling. The I / I ₀ ratio was different from each other as 1.69 and 0.79 for the perborate for TBHP. The signaling to HOCl in selective TCCA signaling by the coumarin oxime may not be a real problem because TCCA is commonly used as a single constituent oxidant in many applications. In this example, attempts were made to obtain signaling conditions that could distinguish TCCA from HOCl, but failed. This may be due to the fact that TCCA in aqueous solution generates HOCl as the active oxidant. In the meantime, the UV-vis absorption properties of coumarin oxime compounds are not useful for the determination of TCCA, since TCCA did not induce any diagnostic changes in the spectral characteristics of the coumarin oxime (FIG. 3).

This signaling is because the oxime moiety of coumarin oxime is oxidatively converted to coumarin carbonyl group. The ¹ H NMR spectrum of the pure reaction product obtained by treating the coumarin oxime containing TCCA was the same as the ¹ H NMR spectrum of ethoxy coumarin (FIG. 4). In the ¹ H NMR spectrum, the resonance for the 3-H and 4-H proton adjacent to the oxime group of the coumarin oxime is significantly shifted to the down field (7.63 ppm and 7.36 ppm). Conversion of coumarin oxime to oxime carbonyl form was also measured by ¹³ C NMR spectroscopy (Figure 5).

Coumarin oxime showed TCCA-selective signaling properties in the presence of common metal ions. Alkali, alkaline earth, and representative transition metal ions were studied, and the fluorescence intensity ratio I / I ₀ at 392 nm varied in a narrow range from 0.93 for Mg ² ⁺ to 1.44 for Ag ⁺ ions (Figure 6) . In addition, the oximes often responded negligible to the anionic tangent. The I / I ₀ ratio, F ^- about 1.02, and HCO ₃ ^- was repeated variation in the limited range of 4.43 to the anion (Fig. 7).

To confirm the practical applicability of the method performed in this example, the selective signaling of the coumarin oxime to TCCA was tested under competitive conditions. TCCA-selective signaling of the coumarin oxime does not have a significant effect in the presence of metal ions or anions that are commonly encountered as background compounds (Figs. 8 and 9).

This experiment means that coumarin oxime can often be used as a TCCA-selective fluorescent probe in the presence of metal ions and anions in contact with environmental samples. The stability of the probe was satisfactory at pH 3 and pH 10, and the fluorescence was not affected by the pH change. However, TCCA signaling increased with increasing pH of the solution and did not significantly change in the basic medium of pH 8 to pH 10 (FIG. 10). In addition, TCCA signaling by coumarin oxime was fast and complete within 1 minute after sample preparation (FIG. 11).

Quantitative signaling of coumarin oxime was studied by fluorescence titration of TCCA (FIG. 12). The emission intensity at 392 nm steadily increased with increasing TCCA concentration and was shown in the illustration of FIG. Plotting of fluorescence intensity at 392 nm appeared as a useful calibration graph up to 3.0 x 10 ^-6 M, just like the function of TCCA concentration. From the concentration dependent signaling reaction, the detection limit of coumarin oxime for the determination of TCCA was measured as 7.58 x 10 <" ⁷ > M in a 90% aqueous acetonitrile solution.

Finally, application of the coumarin oxime probe as a practically useful test strip was attempted (Fig. 13 (a) and (b)). Coumarin oxime probe in aqueous acetonitrile (5 mM) was applied on TLC plates (silica gel). Addition of various concentrations of TCCA solution on the plate caused enhancement of blue fluorescence. The obtained intensity profile means that the probe can easily reduce the TCCA signal to 10 ^-5 M without any complicated equipment.

In summary, a new trichloroisocyanuric acid (TCCA) -elective probe based on coumarin oxime was prepared. The oxime derivatives of ethoxycomarine exhibited a prominent fluorescence-on type signaling towards the industrially important chloramine TCCA due to the oxime-carbonyl conversion. In addition, the selective signaling was achieved in the presence of common metal ions and anions as background compounds. In addition, TCCA-selective signaling was possible in the presence of other commonly used substantial oxidants such as peracids and peroxides.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims

A composition for detecting trichlorosyanooic acid comprising a coumarin oxime compound represented by the following formula
[Chemical Formula 1]

In Formula 1,
R ₁ is optionally substituted alkyl groups of linear or branched C _1-6, C _1-6 alkoxy group which may be substituted, the alkynyl group, or a C _6-12 which may be substituted with _2-7 of C Aryl group.

The method according to claim 1,
A composition for detecting trichlorosyanooic acid further comprising a metal ion or an anion.

A method for detecting trichlorosanooic acid according to claim 1 or 2,
A method for detecting trichlorosyanooic acid.

The method of claim 3,
Wherein the oxime of the coumarin oxime is converted to a carbonyl group to detect the trichlorosyanooic acid.