KR101381578B1 - Compound for palladium detection and preparation method thereof - Google Patents

Abstract

The present invention relates to a compound for detecting palladium and a preparation method thereof. The compound for detecting palladium and the preparation method thereof according to the present invention significantly reduces reaction time for detecting palladium, does not need additional additives such as a catalyst, and reduces costs for detecting palladium since detection at room temperature is possible. Moreover, the compound of the present invention serves as an excellent chemical sensor for detecting palladium, since the compound has high selectivity and sensitivity to palladium.

Description

Compound for detecting palladium and preparation method thereof

The present invention relates to a compound for detecting palladium and a method for preparing the same, and more particularly to a compound for detecting palladium and a method for producing the same having a rapid reaction and high selectivity and sensitivity to palladium.

Palladium, one of the platinum group metals, is a platinum element belonging to the 5th cycle of the group 10 of the periodic table, and has an atomic number of 46, an atomic weight of 106.42 g / mol, a melting point of 1554.9 ° C, a boiling point of 2,963 ° C and a density of 12.023 g / cm 3. It is a silver white metal with good malleability and ductility, and forms an alloy with almost all metals. In addition, since it absorbs hydrogen well and releases it, its activity is also strong, so it is used for the purification of hydrogen. Since it has a strong reducing effect, it is also important as an organic synthesis or an exhaust gas catalyst for automobiles. It is also cheaper than platinum and is lighter and harder, so it is widely used in surgical instruments, fuel cell materials, dental materials, thermometers and decorative precious metals for advanced surgery.

However, such palladium corresponds to heavy metals as transition metals, and palladium, which is widely used, has a problem that palladium, which is a heavy metal, remains when it is left in the product with the expansion of application to medicine, cosmetics, and electronic materials.

Therefore, researches are actively searching for a method for selectively detecting palladium using chemical sensors. Conventionally, it has been detected by atomic absorption spectroscopy, plasma emission spectroscopy, solid state microextraction high performance liquid chromatography, X-ray fluorescence, etc., but this has a problem that the apparatus cost is too expensive or the conditions are too strict for detection. Thus, in order to overcome this problem, research is being conducted on a fluorescent sensitive chemical sensor which can be detected at relatively low cost and in a relaxed condition. However, even in the case of such a fluorescence-sensitive chemical sensor, a long time is required to achieve the saturation point, and there is a problem that the detection conditions are still strict due to a problem of adding an additive such as a catalyst or adding a condition such as heating.

The present invention has been made to solve the above-described problems, the object of the present invention is to reduce the reaction time, do not need to add additional additives such as catalyst, detectable at room temperature, and also has a high selectivity to palladium It is to provide a compound for detecting palladium having a sensitivity and a method of manufacturing the same.

The compound for detecting palladium according to an aspect of the present invention for solving the above problems is characterized in that represented by the formula (1).

[Chemical Formula 1]

In addition, the compound represented by Formula 1 is characterized in that the thiophene methylamine (thiophenemethylamine) is substituted.

In addition, the compound containing palladium detected by the compound represented by Formula 1 is Pd ⁰ [Pd (PPh ₃ ) ₄ ], Pd ^{2 +} [PdCl ₂ , PdBr ₂ , Pd (OAc) ₂ , PdCl ₂ (PPh ₃ ) ₃ ] and Pd ^{4 +} [K ₂ PdCl ₆ ].

In addition, when the compound represented by Formula 1 reacts with palladium to develop color, the maximum peak of the color intensity is formed between 575 nm and 600 nm.

In addition, the minimum detection limit of the palladium in detecting the compound represented by the formula 1 reacts with palladium is characterized in that 0.05μM (Pd content = 5.3 gL ^-1 ).

Method for producing a compound for detecting palladium according to another feature of the present invention

1) synthesizing 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde by mixing K ₂ CO ₃ in a solution of acetonitrile and 2-Hydroxy-5- (hydroxymethyl) benzaldehyde;

2) Phosphorus tribromide was added to a solution of dichromethane and 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 1), followed by mixing sodium hydrogencarbonate. Synthesizing 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde;

3) 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 2) with K ₂ CO ₃ was added to a solution in which resorupine sodium salt was mixed with dimethylformamide (DMF). Mixing to synthesize 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde; And

4) 2-thiophenemethylamine, CH ₂ Cl ₂ and sodium tria to 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 3) 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin- represented by the following Chemical Formula 1 by mixing sodium triacetoxyborohydride Synthesizing 3-one;

.

[Chemical Formula 1]

In addition, in step 1), the 2-Hydroxy-5- (hydroxymethyl) benzaldehyde is mixed with 3.7 to 4.0 mmol in the solution, and the solution is characterized in that K ₂ CO ₃ is mixed with 7.5 to 8 mmol.

In addition, in step 2), 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is characterized in that the mixture is made of 3.0 ~ 3.5mmol.

In addition, in step 3), the resorphin sodium salt is mixed with 0.5 to 1 mmol, the K ₂ CO ₃ is mixed with 0.8 to 1.2 mmol, and 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde is Characterized in that the mixture is made of 1.8 ~ 2.2mmol.

In addition, in step 4), the 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde and the thiophenmethylamine are mixed in 0.2 to 0.3 mmol, respectively. Sodium triacetoxyborohydride (sodium triacetoxyborohydride) is characterized in that the mixture is made of 0.3 ~ 0.4 mmol.

The palladium detecting compound according to the present invention and a method for producing the same have an effect of significantly reducing the reaction time for detecting palladium, and do not need to add additional additives such as a catalyst, and can be detected at room temperature, thereby resulting in palladium detection. This has the effect of significantly lowering the cost. In addition, it is possible to provide a compound for detecting palladium having an effect having a particularly high selectivity and sensitivity to palladium, the compound according to the invention can serve as an excellent chemical sensor for detecting palladium.

1 is a graph showing whether the compound synthesized by the example shows a color reaction for palladium.
Figure 2 is a picture showing the color change when the palladium is added to the solution containing the compound synthesized by the embodiment.
3 is a graph showing that the detection of palladium is improved due to the introduction of thiophene methyl sidearm into the compound synthesized by the example.
4 is a graph showing the fluorescence emission intensity of the compound according to the example according to the concentration of palladium.
5 is a graph showing that the compound synthesized by the example in the range of 0 ~ 5.0μM fluorescence emission in linear proportion to the concentration of Pd ^{2 +} .
FIG. 6 is a graph showing that a compound synthesized according to an example is a compound that selectively reacts with palladium to detect various metals.
FIG. 7 is a graph showing whether the compounds synthesized by the examples are selective for one or more palladium groups.
8 is a graph showing that the compounds synthesized by the examples detect palladium by the reaction mechanism according to the present invention.
9 is a graph showing whether the compound synthesized according to the example also changes in reactivity with a range of changes in pH.
FIG. 10 is a diagram showing an optimized structure of a compound synthesized by an example and a compound of a comparative example and a bonding structure with palladium.

Accordingly, the present inventors have made diligent research efforts to develop a palladium detection compound and a method for producing the same, which are excellent in selectivity and sensitivity to palladium and reduce the time required for detection even without strictly limiting the conditions for palladium detection. The present invention was completed by discovering a compound for detecting palladium according to the present invention and a method of preparing the same.

That is, the present inventors have developed a compound that combines a resorufin residue and an O-proparyl unit as a dual color and fluorescence stoichiometry for rapid detection of palladium species. As the molecular scaffold, a strong pink fluorescent dye, resorupin, was chosen as the signaling unit, and the O-proparyl unit was the trigger because of its strong reaction to palladium species in all typical oxidation states (0, +2 and +4). It was attached to the scaffold as part. Finally, thiophenemethylamine was substituted at the o-position of the O-proparyl moiety to increase the reactivity with palladium species.

Specifically, the compound for detecting palladium according to the present invention may be represented by the following Chemical Formula 1.

The compound represented by Chemical Formula 1 corresponds to a compound that detects palladium quickly and accurately without the need for other catalysts.

In addition, the compound represented by Chemical Formula 1 may be formed by the substitution of thiophenemethylamine. Substitution of the thiophenmethylamine may increase reactivity to palladium groups.

In addition, the compound containing palladium detected by the compound represented by Formula 1 is Pd ⁰ [Pd (PPh ₃ ) ₄ ], Pd ^{2 +} [PdCl ₂ , PdBr ₂ , Pd (OAc) ₂ , PdCl ₂ (PPh ₃ ) ₃ ] and Pd ^{4 +} [K ₂ PdCl ₆ ].

In addition, the compound represented by Formula 1 is characterized in that the palladium is detected by reacting with palladium to emit a fluorescent material, the fluorescent material may be preferably resorufin (Resorufin). The resorrupine is a fluorescent dye and in the present invention corresponds to a signaling unit that confirms whether palladium is detected.

Detection of palladium by the compound represented by Formula 1 may be to detect the palladium by the reaction represented by the following Scheme 1.

[Reaction Scheme 1]

The compound represented by Chemical Formula 1 by Scheme 1 is to fluoresce as the hydroxyl group of the resorrupine alkylated. As a preferred embodiment, when PdCl ₂ is added to the solution containing the compound represented by Chemical Formula 1, O-proparyl moiety is depropylated from the compound represented by Chemical Formula 1, and then 1, The 6-removal is released and the free resorphin is released, resulting in both calorimeter and fluorescence changes. The O-proparyl moiety can induce a strong reaction to all palladium species (0, +2 and +4).

When the compound represented by Chemical Formula 1 reacts with palladium to color, a maximum peak of color intensity is formed between 575 nm and 600 nm.

In addition, the minimum detection limit of palladium in detecting the compound represented by Formula 1 by reacting with palladium is 0.05 μM (Pd content = 5.3 gL ⁻¹ ).

Therefore, in the case of detecting palladium by the compound represented by Chemical Formula 1, it is possible to provide a compound and a chemical sensor which are selective to palladium without adding a special catalyst and have high sensitivity. This enables fluorescence coloration upon palladium detection, allowing the naked eye to identify whether palladium is detected by the compound of Formula 1, and enable simple and rapid palladium detection without strict conditions.

Method for producing a compound for detecting palladium according to another feature of the present invention

1) synthesizing 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde by mixing K ₂ CO ₃ in a solution of acetonitrile and 2-Hydroxy-5- (hydroxymethyl) benzaldehyde;

2) Phosphorus tribromide was added to a solution of dichromethane and 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 1), followed by mixing sodium hydrogencarbonate. Synthesizing 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde;

3) 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 2) with K ₂ CO ₃ was added to a solution in which resorupine sodium salt was mixed with dimethylformamide (DMF). Mixing to synthesize 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde; And

4) 2-thiophenemethylamine, CH ₂ Cl ₂ and sodium tria to 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 3) 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin- represented by the following Chemical Formula 1 by mixing sodium triacetoxyborohydride Synthesizing 3-one;

.

[Chemical Formula 1]

The method for preparing the palladium detecting compound is not particularly limited thereto and may include a reaction according to [Scheme 2] as a preferred embodiment.

[Reaction Scheme 2]

Looking at the production method of the compound for detecting palladium according to the present invention in more detail, the acetonitrile in step 1) is preferably 1-3 equivalents. In addition, the solution of acetonitrile and 2-Hydroxy-5- (hydroxymethyl) benzaldehyde is mixed with the 2-Hydroxy-5- (hydroxymethyl) benzaldehyde in acetonitrile, preferably 3.7 ~ 4.0mmol, K in the solution ₂ CO ₃ is preferably characterized in that the mixture is made of 7.5 to 8 mmol. When 2-Hydroxy-5- (hydroxymethyl) benzaldehyde is mixed to less than 3.7 mmol or K ₂ CO ₃ is mixed to less than 7.5 mmol, 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is sufficiently It is not preferable because it cannot be synthesized, and when 2-Hydroxy-5- (hydroxymethyl) benzaldehyde is mixed in excess of 4.0 mmol, or when K ₂ CO ₃ is mixed in excess of 8 mmol, an excessive amount is achieved despite sufficient synthesis. It is not preferable because it is inefficient to use. In addition, the mixture is preferably mixed by stirring at 25 ~ 75 ℃ for 40 to 55 hours can be sufficiently synthesized 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde.

In the solution mixed by step 2), 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is preferably mixed at 3.0 to 3.5 mmol. When the 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is mixed at less than 3.0 mmol, 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde cannot be sufficiently synthesized, which is not preferable. In addition, when the 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is mixed in excess of 3.5 mmol, it is not preferable because excessive amounts are used despite being sufficiently synthesized. In addition, the mixing is preferable because it can synthesize 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde which is sufficient to be stirred and mixed for 10 to 15 hours at a temperature of -1 to 1 ℃.

In the step 3), the DMF is preferably 1 to 2 equivalents, and the resorphurine sodium salt is preferably mixed with 0.5 to 1 mmol in the DMF, and the K ₂ CO ₃ is mixed with 0.8 to 1.2 mmol. Preferably, the 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde is preferably mixed with 1.8 to 2.2 mmol. When the resorupin sodium salt, K ₂ CO ₃ and 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde, respectively, are mixed below the lower limit of the numerical range, sufficient 5-((3-oxo-3H -phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde cannot be synthesized, which is not preferable, and the resorrupine sodium salt, K ₂ CO ₃ and 5- (bromomethyl) -2- (prop In the case where -2-ynyloxy) benzaldehyde is mixed in excess of the upper limit of the numerical range, it is not preferable because excessive amounts are mixed because of sufficient synthesis. In addition, the mixing is preferably 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde which is sufficient to stir for 1 to 3 days at room temperature. It is preferable because it can synthesize | combine.

In step 4), 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde and thiophenmethylamine are preferably mixed in 0.2 to 0.3 mmol, respectively. If less than the lower limit of the numerical range, sufficient 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin-3-one can be synthesized. It is not preferable because it is not preferable, and in the case of exceeding the upper limit of the numerical range, an excessive amount is used in spite of sufficient synthesis, which is inefficient. In addition, in step 4), sodium triacetoxyborohydride is preferably mixed with 0.3 to 0.4 mmol, in the case of less than the lower limit of the numerical range, sufficient 7- (4- (prop-2-ynyloxy) It is not desirable to synthesize -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin-3-one, and if the upper limit of the above numerical range is exceeded, an excessive amount may be used despite sufficient synthesis. It is not preferable because it is inefficient to use. In addition, the mixing of step 4) is carried out by stirring for 1 to 2 hours under a nitrogen (N ₂ ) atmosphere, 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl ) benzyloxy) -3H-phenoxazin-3-one is preferable since it can be synthesized.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example

Synthesis of Compound

For the detection of palladium, a compound corresponding to a new and effective chemical stoichiometry exhibiting fast reaction and high selectivity and sensitivity even under mild conditions was newly synthesized through the reactions and conditions as shown in [Scheme 3].

[Reaction Scheme 3]

The synthesis process of the compound No. 1 according to the present Example synthesized by the above [Reaction Scheme 3] will be described below in more detail.

1. 5- ( hydroxymethyl )-2-( prop -2- ynyloxy ) benzaldehyde  (3) synthetic

2-Hydroxy-5- (hydroxymethyl) benzaldehyde was prepared by purchasing a commercially available salicylaldehyde (Aldrich, S356, CAS: 90-02-8). At this time, 2 equivalents of K ₂ CO ₃ (1.07 g, 7.76 mmol) was added to the solution containing 2-hydroxy-5- (hydroxymethyl) benzaldehyde (590 mg, 3.88 mmol) in acetonitrile at room temperature. It was then stirred for 1 hour and then dropwise treated with toluene (508 mg, 4.27 mmol, 1.1 equiv) with 80% by weight of a solution of proparyl bromide. The reacted mixture was then heat treated at 50 ° C. for 48 hours and then cooled, which was then filtered and concentrated in vacuo again. Flash chromatography was used to purify compound 3 (555 mg, 75% yield) as colorless oil. ¹ H and ¹³ C NMR spectra of the purified compound 3 were as follows.

¹ H NMR (CDCl ₃ ) δ (ppm): δ 2.57 (t, J = 2.4 Hz, 1H), 4.68 (d, J = 3.4 Hz, 2H), 4.84 (d, J = 2.4 Hz, 2H), 7.13 (d, J = 8.5 Hz, 1H), 7.61-7.63 (m, 1H), 7.84 (d, J = 2.3 Hz, 1H), 10.47 (s, 1H); ¹³ C NMR (CDCl ₃ ) δ (ppm): 56.71, 64.52, 76.80, 77.79, 113.74, 125.48, 127.32, 134.52, 134.79, 159.43, 189.69; ESI-MS: m / z = 189.10 [M ⁻ H] ⁻ .

2. 5- ( bromomethyl )-2-( prop -2- ynyloxy ) benzaldehyde  (4) synthetic

Phosphorus tribromide (0.3 mL) was slowly added at 0 ° C. to a solution containing compound 3 (610 mg, 3.2 mmol) in dichromethane (50 mL). After stirring for 12 hours, the reacted mixture was mixed with sodium bicarbonate containing water. The solvent was removed in vacuo from the organic phase and compound 4 was purified as a colorless solid (600 mg, 74% yield) using flash chromatography. ¹ H and ¹³ C NMR spectra of the purified compound 4 were as follows.

¹ H NMR (CDCl ₃ ): δ 2.59 (t, J = 2.4 Hz, 1H), 4.49 (s, 2H), 4.85 (d, J = 2.4 Hz, 2H), 7.12 (d, J = 8.6 Hz, 1H ), 7.62 (dd, J = 2.5 Hz, 1 H), 7.88 (d, J = 2.5 Hz, 1 H), 10.45 (s, 1 H). ¹³ C NMR (DMSO-d6): δ 34.29, 57.25, 79.13, 79.94, 115.41, 125.29, 129.26, 132.07, 137.68, 159.87, 189.28.

3. Synthesis of 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde (5)

1.5 equivalents of K ₂ CO ₃ (141 mg, 1.02 mmol) and 3 equivalents of Compound 4 (514 mg, 2.04 mmol) were added to the solution containing the resorupin sodium salt (160 mg, 0.68 mmol) in DMF. The reaction mixture was stirred at room temperature for 2 days. After evaporating it to dryness, the residue was partitioned between CH ₂ Cl ₂ and brine. The organisms contained therein were washed with water. And it was dried with anhydrous Na ₂ SO ₄ . Flash 5 was also used to purify compound 5 (140 mg, 53% yield) as an orange red solid. ¹ H and ¹³ C NMR spectra of the purified compound 5 were as follows.

¹ H NMR (DMSO-d6): δ 3.70 (t, J = 2.3 Hz, 1H), 5.03 (d, J = 2.3 Hz, 2H), 5.29 (s, 2H), 6.27 (d, J = 2.0 Hz, 1H), 6.77-6.80 (m, 1H), 7.12-7.15 (m, 1H), 7.21 (d, J = 2.6Hz, 1H), 7.36 (d, J = 8.6Hz, 1H), 7.53 (d, J = 9.8 Hz, 1H), 7.78-7.85 (m, 3H), 10.35 (s, 1H). ¹³ C NMR (DMSO-d6): δ 57.25, 70.00, 79.21, 79.91, 101.89, 106.33, 114.97, 115.30, 125.26, 128.26, 128.71, 129.90, 132.03, 134.43, 135.61, 136.65, 145.89, 145.99, 150.40, 160.01 162.82, 186.03, 189.49; ESI-MS: m / z = 384.10 [M ⁻ H] ⁻ .

4. Synthesis of 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin-3-one (1)

Compound 5 (100 mg, 0.26 mmol) and 2-thiophenemethylamine (30 mg, 0.26 mmol) were mixed with CH ₂ Cl ₂ (5 mL). And it was treated with sodium triacetoxyborohydride (77 mg, 0.36 mmol, 1.4 equivalents). The reaction mixture was stirred for 1.5 hours at room temperature under a nitrogen (N ₂ ) atmosphere. This mixture then quenched the reaction by adding water saturated NaHCO ₃ . And this product was extracted with CH ₂ Cl ₂ . The organisms so contained were dried over anhydrous MgSO ₄ . Then compound 1 (30 mg, 24% yield) was purified as a light brown solid using flash chromatography (MeOH / CH ₂ Cl ₂ = 0% to 5%). ¹ H and ¹³ C NMR spectra of the purified compound ¹ were as follows.

¹ H NMR (CDCl ₃ ): δ 2.52 (t, J = 2.3 Hz, 1H), 3.89 (s, 2H), 3.99 (s, 2H), 4.76 (d, J = 2.3 Hz, 2H), 5.10 (s , 2H), 6.32 (d, J = 2.0 Hz, 1H), 6.82-6.89 (m, 2H), 6.94-6.97 (m, 2H), 6.99-7.04 (m, 2H), 7.21-7.23 (m, 1H ), 7.32-7.36 (m, 1H), 7.39-7.44 (m, 2H), 7.71 (d, J = 8.9 Hz, 1H). ¹³ C NMR (CDCl ₃ ): δ 47.63, 47.97, 56.00, 70.64, 75.88, 78.31, 101.00, 106.72, 112.07, 114.34, 124.44, 124.91, 126.61, 127.86, 128.12, 128.43, 129.26, 139.84, 131.59, 134.22. , 144.07, 145.57, 145.59, 149.81, 155.82, 162.72, 186.33. ESI-MS: m / z = 481.15 [M ⁻ H] ⁻ .

By the above method, the first compound, which is the compound to be finally synthesized in the present invention, was finally synthesized. In addition, the preliminary preparation for carrying out the experiment of the following Experimental Example on the preparation of the preparation and how effectively the compound thus synthesized to detect the palladium was performed as follows.

<Instruments and reagents>

In the following experiments, all fluorescence and UV / Vis absorption spectra were recorded on Shimadzu RF-5301PC and Agilent 8453 spectrophotometers, respectively. All ¹ H and ¹³ C NMR spectra were collected by dissolving in CDCl ₃ or DMSOd-6 in a Varian 300 MHz and 400 MHz spectrometer. All chemical shifts are reported in ppm values using the residual proton signal peak of TMS as an internal reference. ESI mass spectral analysis was performed using LC / MS-2020 series (Shimadzu). All analytes were purchased from Aldrich and used upon receipt. All solvents were purchased with analytical reagent grades from Duksan Pure Chemical Co., Ltd. All DMSO for spectral detection was HPLC reagent grade free of fluorescent impurities. H ₂ O was deionized water.

<Observation of Synthesized Compound>

The detailed chemical approach of the compounds synthesized by this example and the comparative examples below is shown in Electronic Supplemental Information (ESI). All chemical structures of the compounds were verified by mass spectrometry, ¹ H NMR and ¹³ C NMR spectroscopy, which can be seen in ESI.

< Mostock  Preparation of the Solution>

To Al ^{3 +} in the experimental ^{examples, Cd 2 +, Co 2 +} , Cu 2 +, Fe 2 +, Fe 3 +, Hg 2 +, Ni 2 perchlorate of ⁺ and Zn ^{2 +,} nitrates of Ag ^+, and Cr ^{+ 3,} was prepared in distilled water to a chloride salt of the parent stock solution of Mn ^{2 +} (10 mM) ² times. Parent stock solutions of PdCl ₂ (5.0 mM), Pd (OAc) ₂ (1.0 mM) and K ₂ PdCl ₆ (1.0 mM) were prepared in a mixture of brine and methanol (3: 1, v: v). Mostok solutions of stoichiometry 1 (1.0 mM), Pd (PPh ₃ ) ₄ (1.0 mM), PtCl ₂ (5.0 mM) and RuCl ₃ (5.0 mM) were prepared in DMSO.

General procedure for the study of fluorescence in solution

Typically, 20 μL of the metered stock solution is placed in a test tube, each aliquot of the analyte stock is added in appropriate portions, and the solution is added to 4 mL of MeOH / PBS (pH = 7.4, 10 mM) solution (8: 2, v: v). Dilution to prepare a test solution. All fluorescence spectra were measured by excitation at 550 nm and the excitation and emission slit widths were both 1.5 nm. UV / Vis and fluorescence experiments were performed at room temperature using 20 μM and 5 μM of the compounds synthesized by this example in MeOH / PBS (pH = 7.4, 10 mM) solution (8: 2, v: v) after the addition of various analytes, respectively. This was done for 30 minutes (except for time-dependent experiments).

Comparative Example

Unlike the usual example, compound 2 was synthesized without substituting thiophenemethylamine as the comparative example.

[Reaction Scheme 4]

Compound No. 2 was prepared according to the literature for a solution containing the resolupin sodium salt in DMF, 1.5 equivalents of K ₂ CO ₃ (141 mg, 1.02 mmol) and 1- (Bromomethyl) -4- (2-propynyloxy) benzene ( 457 mg, 2.04 mmol) 3 equivalents were added. The reaction mixture was stirred at room temperature for 2 days. After evaporating it to dryness, the residue was partitioned between CH ₂ Cl ₂ and brine. The organisms contained herein were washed with water. And it was dried over anhydrous Na ₂ SO ₄ . Flash chromatography was used to purify compound 2 as a Reddish Brown solid. The ¹ H and ¹³ C NMR spectra of the purified compound 2 were as follows.

¹ H NMR (CDCl ₃ ): δ 2.54 (t, J = 2.4 Hz, 1H), 4.72 (d, J = 2.3 Hz, 2H), 5.11 (s, 2H), 6.33 (d, J = 2.0 Hz, 1H ), 6.82-6.89 (m, 2H), 6.99-7.05 (m, 3H), 7.38-7.45 (m, 3H), 7.72 (d, J = 8.9 Hz, 1H). ¹³ C NMR (DMSO-d6): δ 56.05, 70.73, 79.01, 79.86, 101.81, 106.30, 115.04, 115.54, 128.62, 129.28, 130.51, 132.00, 134.38, 135.61, 145.86, 145.92, 150.42, 157.85, 163.06, 18.6.0 ESI-MS: m / z = 356.10 [M ⁻ H] ⁻ .

Experimental Example

< Experimental Example  1: for palladium Color  Signal Behavior Investigation Experiment>

The next experiment was carried out with the most toxic PdCl ₂ selected as the palladium species to be used in this experiment. First, the color development signal behavior of the compound synthesized by the example for PdCl2 was investigated with varying concentrations in MeOH / PBS (pH = 7.4, 10 mM) solution (8: 2, v: v). The results are shown in FIGS. 1 and 2 below.

As can be seen in FIG. 1, the compound synthesized by the Example (black) without any substance added showed a moderate UV-Vis absorption at 471 nm, and the flat part appeared at around 391 nm, but 576 nm. There was little absorption in. However, when increasing the amount of PdCl ₂ (solution color changes from pale yellow to pale pink and increases the amount of PdCl ₂ , it changes from pale pink to dark pink. In addition, the direction of the arrow in FIG. 1 is the amount of PdCl ₂ . The absorption peak of Compound 1 formed a peak once at approximately 471 nm and then a maximum peak at approximately 576 nm. As a result, it was confirmed that the maximum peak of the color intensity was formed between 575 nm and 600 nm. Meanwhile, as can be seen in the left (a) picture of FIG. ₂ , when PdCl ₂ was added, the color was changed from light yellow to pink. In addition, as shown in the right (b) photo of FIG. 2, when the illumination was performed using a handhold UV lamp, a dramatic change in color from dark red to crimson was observed. Therefore, Experimental Example 1 confirms that the compound synthesized by the Example shows a specific color signal for the palladium species while forming a maximum peak at around 575 nm to 600 nm for the palladium species.

< Experimental Example  2: Thiophenmethyl Of thiophenemethylamine  Experiment showing substitution effect>

Experiments were conducted to determine the difference in effect due to the substitution of thiophenemethylamine with the compound synthesized by the above example and the compound of the comparative example. Its experiment was measured by monitoring the fluorescence changes seen in the compounds synthesized by the examples (5.0 μM) and the comparative examples (5.0 μM) with and without PdCl ₂ as a function of time. 3 is shown.

As can be seen in FIG. 3, in the absence of PdCl ₂ , no significant fluorescence change was observed in both the compounds synthesized by the Examples and Comparative Examples.

On the other hand, it is related to the presence of PdCl ₂ , and when 1.0 equivalent of PdCl ₂ was added to the solution mixed with the compound synthesized by the comparative example, the fluorescence intensity increased only very slowly at 586 nm. Treatment with thicker PdCl ₂ (50 μM) accelerated the increase in fluorescence intensity but required several hours to achieve saturation. On the other hand, when 1.0 equivalent of PdCl ₂ was added to the solution mixed with the compound synthesized in Example under the same conditions, a rapid increase in fluorescence intensity appeared, and the fluorescence intensity reached flatness within 30 minutes. Pseudo-first-order rate constants when the compounds of Examples and Comparative Examples were reacted with PdCl ₂ were estimated from fitting time-dependent fluorescence changes to single exponential growth (ESI). Estimate of the rate constants, respectively, and 157.51 ± 15.06 18.93 ± 1.76 M ^-1 s ^{- 1} was.

Therefore, the results according to the present experimental example confirmed that the compound synthesized by the example as substituted with thiophenemethylamine (PdCl ₂ ) significantly increased (approximately 8 times).

< Experimental Example  3: In the embodiment  Of compounds synthesized by PdCl2  Fluorescence Titration Experiments for Concentration>

Fluorescence titration experiments of PdCl ₂ were carried out using a 5.0 μM solution of the compound of Example in a MeOH / PBS (pH = 7.4, 10 mM) solution (8: 2, v: v). Its experiment was determined by monitoring the fluorescence intensity of each solution from 30 minutes after adding PdCl ₂ to the solution. The results of this experiment are shown in Figures 4 and 5 below.

As can be seen in FIG. 4 below, the fluorescence emission intensity of the compound according to the example was saturated when Pd ^{2 +} 1.0 equivalent was added, and the increment was approximately 24 times (the fluorescence intensity forming the maximum peak in FIG. As the concentration increases, the concentration of PdCl ₂ increases, and the curve having the maximum peak at the top thereof is the curve corresponding to Pd ^{2 +} 1.0 equivalent). On the other hand and the observed fluorescence intensity (586nm) is in the range of 0 ~ 5.0μM linearly proportional to the concentration of Pd ^{+ 2} (see Fig. 5). In addition, the minimum detection limit of the compounds synthesized by the examples for PdCl ₂ was calculated to be 0.05 μM (Pd content = 5.3 gL ⁻¹ ) (ESI), which is the body's palladium content (from the saliva samples taken in the morning). 10.6 ± 7.4 gL ⁻¹ ).

< Experimental Example  4: In the embodiment  Palladium selectivity measurement experiment of compound synthesized by

An experiment was conducted to confirm that the compound synthesized according to the example selectively showed a fluorescent reaction with respect to palladium. Ag ⁺ , Al ^{3 +} , Cd ^{2 +} , Co ^{2 +} , Cr ^{3 +} , Cu ^{2 +} , Fe ^{2 +} , Fe ^{3 +} , Hg ²⁺ , Mn ^{2 +} , Ni ^{2 +} , Pt ^{2 +} , Ru ^{3 +} , and followed by the addition of various metal ions (50.0μM), such as Zn ^{+ 2,} further addition of PdCl ₂ (5.0μM) was measured that the dramatic increase in the fluorescence intensity, it was confirmed that this selectivity for palladium over. The results are shown in FIG.

As can be seen in Figure 6 Ag ⁺ , Al ^{3 +} , Cd ^{2 +} , Co ^{2 +} , Cr ^{3 +} , Cu ^{2 +} , Fe ²⁺ , Fe ^{3 +} , Hg ^{2 +} , Mn ^{2 +} , Ni ^{2 When} various metal ions (50.0 μM) such as ⁺ , Pt ^{2 +} , Ru ^{3 +} , and Zn ^{2 +} were added, no significant fluorescence intensity change was observed (red bar in FIG. 6) and PdCl ₂ (5.0 μM) Further addition resulted in a dramatic increase in fluorescence intensity (blue bar in FIG. 6). The effect when present in the embodiment the compound is other metal ions Pd ^{2 +} extremely exhibit high selectivity, Pd ^{2 +} other metal ions are very high concentrations (10 eq.) Detection of about compared with the synthesis by these results You can see that you did not receive.

< Experimental Example  5: In the embodiment  Measurement experiment whether the compound synthesized by

To prove potential uses, other palladium species [Pd (0): Pd (PPh ₃ ) ₄ ; Pd (II): Pd (OAc) ₂ ; The reaction of the compound synthesized by the Example for Pd (IV): K ₂ PdCl ₆ ] was measured. As shown in (a) to (c) of FIG. 7, the compounds synthesized by the examples of PdCl ₂ (see FIG. 7A) and Pd (OAc) ₂ (see FIG. 7B) Similar reactivity was shown. On the other hand, when reacted with Pd (PPh ₃ ) ₄ , it is slower than other palladium species. This is expected to be due to the mechanism of the Pd catalyst ⁰ in deionized Pro paril screen is different from the to Pd2 + and Pd ^{+ 4.} However, the reactivity of the compound synthesized by the examples is still higher than that of the comparative example for Pd (PPh ₃ ) ₄ (see FIG. 7C). From these results, it can be seen that the compound synthesized by the metering example shows a remarkably fast reaction and significant fluorescence change for all oxidation states of palladium.

< Experimental Example  6: Reaction Mechanism Verification Experiment>

The compound synthesized by the above Example was conducted to confirm that palladium can be selectively detected by the reaction mechanism according to [Scheme 5].

[Reaction Scheme 5]

Looking at the reaction mechanism according to the [Scheme 5] in detail, the compound synthesized in the embodiment will show a very weak fluorescence as the hydroxyl group of the resorrupine alkylated. In addition, when PdCl ₂ was added to the solution mixed with the compound synthesized by the example, the O-proparyl moiety was depropylated from the compound synthesized by the example, followed by 1,6-removal of p-quinonemethide. As the free resorphin is released, changes occur in both the calorimeter and the fluorometer. In order to confirm this reaction mechanism, the reaction mixture was analyzed by liquid chromatography-mass spectrometry (LC-MS) in this experiment. The results are shown in Figure 8 below.

To the MS spectrum m / z 212.00 [MH] corresponding to the resonance lupine As can be seen in Figure 8 ^(see (a) of Fig. 8) and m / z 254.10 corresponding to p- quinone nonme lactide derivative [M The peak was clearly observed in + Na] ⁺ (see FIG. 8 (b)), and it was confirmed that the reaction was performed by the reaction mechanism according to the above scheme.

< Experimental Example  7: pH Measurement of reaction change by

In addition, an experiment was conducted to determine whether the compound synthesized according to the example also changes in reactivity with a range of changes in pH, and the results thereof are shown in FIG. 9.

As can be seen in Figure 9 below, the reaction of the compound synthesized in the examples was independent of the surrounding pH change. Therefore, changes in the fluorescence of Compound 1 in the presence of Pd ^{2 +} by the present experiment is to verify that it is possible to detect a Pd ^{+ 2} in the pH range of 5-11 by using a chemical-based quantitative.

< Experimental Example  8: pH Measurement of reaction change by

In order to examine in more detail the effect of the compound synthesized by the examples to the substitution with thiophenmethylamine, theoretical calculations were performed based on density function theory (DFT) using the Gaussian 09 program. The optimized structure of the compound synthesized by the examples and the compound of the comparative example is as shown in FIG. 10. The compound synthesized by the examples has a stronger binding capacity than the comparative example was supported by the greater binding energy (calculated on gas) of Compound 1 and Pd species (see Table 1 below). The capture of Pd species by the compound or comparative example synthesized in the solution in solution depends on the combined effect of the binding energy and solvation energy obtained by the Pd-complex. Table 1 shows the Gibbs free energy change (-ΔGsolv) for solvation in methanol (as an example) for the compounds synthesized by the examples and for the comparative examples. Comparative Examples plum energy (-ΔGsolv) for the Pd ^{2 +} ion due to greater solvent accessible space around only slightly greater than the compound synthesized by the embodiment (see Fig. 10), the combination effect is carried out as compared with Comparative Example Example It is much larger in the compound synthesized by, which suggests that the capturing ability of the compound synthesized by the examples in solution is better. The linear relationship between the binding energy (or combination effect) and the reaction rate constant for the reaction of the compound synthesized by the examples and PdCl ₂ with the comparative example shows that the rate at which the palladium species are trapped by the molecules is depropanylated Support the decision phase (the slowest step).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is natural.

Claims (10)

A palladium detection compound, characterized in that represented by the formula (1).
[Chemical Formula 1]

The method according to claim 1,
Compound represented by the formula (1) is a compound for detecting palladium, characterized in that the thiophenemethylamine is substituted.
The method according to claim 1,
Compounds containing palladium detected by the compound represented by Formula 1 are Pd ⁰ [Pd (PPh ₃ ) ₄ ], Pd ^{2 +} [PdCl ₂ , PdBr ₂ , Pd (OAc) ₂ , PdCl ₂ (PPh ₃ ) ₃ ] and Pd ^{4 +} [K ₂ PdCl ₆ ] A compound for detecting palladium, characterized in that at least one compound selected from the group consisting of.
The method according to claim 1,
When the compound represented by Chemical Formula 1 reacts with palladium to develop a color, the maximum peak of the color intensity is formed between 575 nm and 600 nm.
The method according to claim 1,
The minimum detection limit of palladium in detecting the compound represented by the formula (1) by reacting with palladium is 0.05μM (Pd content = 5.3 gL ^-1 ), characterized in that the compound for detecting palladium.
1) synthesizing 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde by mixing K ₂ CO ₃ in a solution of acetonitrile and 2-Hydroxy-5- (hydroxymethyl) benzaldehyde;
2) Phosphorus tribromide was added to a solution of dichromethane and 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 1), followed by mixing sodium hydrogencarbonate. Synthesizing 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde;
3) 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 2) with K ₂ CO ₃ was added to a solution in which resorupine sodium salt was mixed with dimethylformamide (DMF). Mixing to synthesize 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde; And
4) 2-thiophenemethylamine, CH ₂ Cl ₂ and sodium tria to 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde synthesized in step 3) 7- (4- (prop-2-ynyloxy) -3-((thiophen-2-ylmethylamino) methyl) benzyloxy) -3H-phenoxazin- represented by the following Chemical Formula 1 by mixing sodium triacetoxyborohydride Synthesizing 3-one;
Method for producing a compound for detecting palladium comprising a.
[Chemical Formula 1]

The method according to claim 6,
In step 1), the 2-Hydroxy-5- (hydroxymethyl) benzaldehyde is mixed with 3.7 to 4.0 mmol in the solution, and K ₂ CO ₃ is mixed with 7.5 to 8 mmol in the solution for palladium detection. Method for preparing the compound.
The method according to claim 6,
In the step 2), the 5- (hydroxymethyl) -2- (prop-2-ynyloxy) benzaldehyde is a method for producing a palladium detection compound, characterized in that the mixture is made of 3.0 ~ 3.5mmol.
The method according to claim 6,
In step 3) the resorphin sodium salt is mixed with 0.5 ~ 1mmol, the K ₂ CO ₃ is mixed with 0.8 ~ 1.2mmol, the 5- (bromomethyl) -2- (prop-2-ynyloxy) benzaldehyde is 1.8 A method for producing a compound for detecting palladium, characterized in that the mixture is mixed with ~ 2.2mmol.
The method according to claim 6,
In step 4), the 5-((3-oxo-3H-phenoxazin-7-yloxy) methyl) -2- (prop-2-ynyloxy) benzaldehyde and the thiophene methylamine are mixed in 0.2-0.3 mmol, respectively. , Sodium triacetoxyborohydride (sodium triacetoxyborohydride) is a method for producing a compound for detecting palladium, characterized in that the mixture is made of 0.3 ~ 0.4 mmol.

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