JP2005083854A - Reagent for measuring toluene and/or xylene, and toluene and/or xylene measuring method using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reagent simply measuring toluene and/or xylene, and a toluene and/or xylene measuring method using it. <P>SOLUTION: This reagent is used for measuring toluene and/or xylene containing a compound having a structure represented by the general formula [I] as an effective component. In the general formula [1], R<SB>1</SB>and R<SB>2</SB>are mutually independently a 1-10C straight chain or branched chain alkyl group which may be substituted with at least one of a carboxyl group, a hydroxyl group, an amino group, halogen, a sulfonyl group and/or a thiol group, and R<SB>3</SB>, R<SB>4</SB>, R<SB>5</SB>and R<SB>6</SB>are mutually independently a hydrogen atom, a 1-10C straight chain or branched chain alkyl group, an amino group, a nitro group, halogen, a carboxyl group, a hydroxyl group, a sulfonyl group or a thiol group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a reagent for measuring toluene and / or xylene and a method for measuring toluene and / or xylene using the same.

In recent years, health damage such as eye and throat pain caused by a chemical substance of a house interior material called “sick house syndrome” or aggravation of atopic dermatitis has been a problem. Chemical substances associated with sick house syndrome include formaldehyde, toluene, xylene, and paradichlorobenzene. Of these, toluene and xylene are used as solvents and diluents for adhesives and paints, and are added to gasoline as anti-knock agents for engines such as automobiles. There are cases where high concentrations of toluene and xylene, which are far from acceptable levels, have been detected in the atmosphere of their manufacturing processes and products, for example, in new homes, homes after renovation, and even in school environments. For this reason, it is necessary to accurately estimate the concentrations of toluene and xylene in room air and in the atmosphere.

Standard measurement methods, detector tube methods, and the like are used as methods for measuring chemical substances in indoor air that have been used so far. Here, the standard measurement method is to force the room air into contact with an appropriate collection tube using a pump, separate the collected material by HPLC or GC, and then detect a detector such as UV or MS. The detector tube method measures the concentration by passing toluene gas through a glass tube filled with a detector (iodine pentoxide) that changes color by reacting with toluene and reading the discolored region. It is a method to do.

While these methods are expected to provide accurate measurement results, i) requires precise analytical equipment and advanced technology, ii) takes some time to determine results, iii) It has also been pointed out that the substances used in the reaction (solvent, catalyst, etc.) are inappropriate for the environment. On the other hand, there is a rapid increase in demand among consumers or housing producers to know the concentration of the chemical substance that is the cause, and there is an urgent need for new methods to replace existing analyzers and reagents. Yes.

Elke, K .; Jermann, E .; Begerow, J .; Dunemann, L. Journal of Chromatography, A, 826 (2), 191-200, 1998. Przyk, E .; zabiegala, B .; Namiesnik, J. Chemiai Inzynieria Ekologiczna, 8 (8-9), 917-924, 2001.

  The objective of this invention is providing the measuring method of toluene and / or xylene using the reagent for toluene and / or xylene which can measure toluene and / or xylene simply.

  As a result of diligent research, the present inventors have found that when an amine compound having a specific structure reacts with toluene or xylene, a colored compound is produced, and this can be used to measure toluene and / or xylene. With this in mind, the present invention has been completed.

  That is, the present invention provides a reagent for measuring toluene and / or xylene containing a compound having a structure represented by the following general formula [I] as an active ingredient.

（ただし、Ｒ_１及びＲ_２は、互いに独立に、炭素数1から10の直鎖型又は分枝型のアルキル基であり、該アルキル基は、１又は２以上のカルボキシル基、水酸基、アミノ基、ハロゲン、スルホニル基及び／又はチオール基で置換されていてもよく、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、互いに独立に、水素原子、炭素数1から10の直鎖型若しくは分枝型のアルキル基、アミノ基、ニトロ基、ハロゲン、カルボキシル基、水酸基、スルホニル基又はチオール基を示す。）

(However, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group includes one or more carboxyl groups, hydroxyl groups, and amino groups. , Halogen, sulfonyl group and / or thiol group, R ₃ , R ₄ , R ₅ and R ₆ are independently of each other a hydrogen atom, a linear or branched group having 1 to 10 carbon atoms Type alkyl group, amino group, nitro group, halogen, carboxyl group, hydroxyl group, sulfonyl group or thiol group.)

  Moreover, this invention provides the measuring method of toluene and / or xylene including making the reagent of the said invention and a test sample contact, and measuring the produced | generated pigment | dye.

  The present invention provides for the first time a reagent for measuring toluene and / or xylene and a method for measuring toluene and / or xylene using the same, which can easily detect or quantify toluene and / or xylene. The reagent of the present invention does not react with other general-purpose volatile organic compounds such as formaldehyde and is not disturbed by inorganic ions or the like. Therefore, by using the reagent of the present invention, toluene and / or xylene in a test sample can be measured simply and sufficiently accurately.

  As described above, the toluene and / or xylene measuring reagent of the present invention contains the compound represented by the above general formula [I] as an active ingredient.

In the general formula [I], R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group is one or more carboxyl groups, It may be substituted with a hydroxyl group, amino group, halogen, sulfonyl group and / or thiol group. The number of these substituents is preferably not more than the number of carbon atoms, more preferably an alkyl group having no substituent, and particularly preferably a methyl group and an ethyl group.

In general formula [I], R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an amino group, a nitro group, Halogen, carboxyl group, hydroxyl group, sulfonyl group or thiol group is shown. The alkyl group may be substituted with one or more carboxyl groups, hydroxyl groups, amino groups, halogens, sulfonyl groups and / or thiol groups. Of these, a hydrogen atom is preferable.

  In addition, the compound represented by the general formula [I] is known per se, and a known method (for example, the method described in the document Hofslokken NU .; Skattebol L. ACTA CHEMICA SCANDINAVICA, 53, 258-262, 1999.) The synthesis method of a preferable compound is also described in detail in the following examples.

  When the compound represented by the general formula [I] is brought into contact with toluene, it reacts as follows to produce a dye compound.

  In the case of xylene, as described above, the aldehyde group and the methyl group react with each other, and both compounds are bonded by a double bond to produce a dye compound.

  Therefore, toluene and / or xylene in a test sample can be measured by measuring a dye produced by the reaction of the compound represented by the general formula [I] with toluene or xylene. The generated dye has an absorption peak in the wavelength region where the compound represented by the general formula [I] hardly absorbs. Therefore, by measuring the generated dye, toluene and / or xylene in the test sample is measured. can do. That is, for example, the dyes produced in the following examples have an absorption peak near a wavelength of 455 nm and are colored yellow or orange, but the reagent used (p-dimethylaminobenzaldehyde) is around a wavelength of 455 nm. These newly produced yellow or orange dyes can be easily measured, and thereby toluene and / or xylene can be measured. In the present specification, “measurement” is used to include both detection and quantification.

  In the method of the present invention, the above-mentioned compound represented by the general formula [I] is brought into contact with toluene and / or xylene in a test sample to produce the dye.

  The reagent of the present invention can be used in the form of a solution or immobilized on a solid phase. When used as a solution, preferred examples of the solvent include water, ethanol, a mixed solvent of both, and the like, but are not limited thereto, and the active ingredient represented by the general formula [I] can be dissolved. Any solvent that does not interfere with the reaction with toluene and xylene can be used. When used as a solution, the concentration of the active ingredient represented by the general formula [I] in the reagent solution is not particularly limited, and can be appropriately selected according to the type of test sample, the scheduled reaction time, and the like. Usually, the final concentration after mixing with the test sample is about 0.1 to 50 mM, preferably about 1 to 10 mM.

When used as a solution, it is preferable to add an inorganic base such as sodium hydroxide or an organic base such as piperidine as an additive. By adding these bases, the effect of promoting the reaction can be obtained. The concentration of these bases in the reagent solution is not particularly limited, but is usually about 0.1 to 50 mM, preferably about 1 to 10 mM, as the final concentration after mixing with the test sample.

  When the reagent is immobilized on a solid phase, preferred examples of the solid phase include filter paper, silica sheet, alumina sheet and the like. Solid phase immobilization is not particularly limited, but a solution of the active ingredient represented by the general formula [I] (preferred solvent and concentration and preferred additive and the same concentration as above) is impregnated into a solid phase such as filter paper and dried This can be easily achieved. The impregnation can be performed by immersing the solid phase in the solution or spraying the solution on the solid phase.

  The test sample may be any sample to be measured for toluene and / or xylene that may be contained therein, and may be a gas or a liquid. As a test sample, the air etc. in the house which newly gave interior can be illustrated, for example.

  The measurement can be performed by simply contacting the test sample with the reagent of the present invention in the form of a solution or immobilized on a solid phase, and measuring the resulting dye. In the case of detection, whether or not toluene and / or xylene is contained in the test sample can be checked by visually checking whether or not the reagent of the present invention is colored. In the case of quantification, preferably, the produced dye can be quantified by measuring the absorbance at the absorption peak of the produced dye or a wavelength in the vicinity thereof, and as a result, toluene and / or in the test sample can be quantified. Xylene can be quantified. When the reagent is in the form of a solution, the quantification can be performed by measuring the absorbance of the reagent as it is or after diluting it to a concentration suitable for measurement as necessary. In the case of being immobilized on the solid phase, after contact with the test sample, the dye produced on the solid phase is eluted in the solvent, and the absorbance of the obtained solution is measured. be able to. The solvent in this case is not particularly limited, and the above solvent used for preparing a reagent solution can be used.

  The reaction time is not particularly limited and can be appropriately selected according to the toluene and / or xylene concentration in the test sample, the desired measurement sensitivity, etc., but is usually about 20 minutes to 1 hour, preferably about 30 minutes. Good. Also, the reaction temperature is not particularly limited, and it is most convenient and preferable to carry out at room temperature.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.

Synthesis of p-dimethylaminobenzaldehyde

To a 50 ml three-necked flask, add 1.0 g (8.26 mmol) of N, N-dimethylaniline, 20 ml of dry toluene, 0.20 g (0.80 mmol) of tin chloride, and 0.60 g (3.22 mmol) of tri-n-butylamine. Stir for hours at room temperature. After adding 0.48 g (16.12 mmol) of paraformaldehyde, the mixture was stirred at 100 ° C. for 12 hours. The contents were poured into ice water, adjusted to pH 7 with 1N hydrochloric acid, and extracted with ether. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (SiO ₂ , CH ₂ Cl ₂ ) to obtain the target compound. Identification was performed using ¹ H-NMR and ESI-TOFMS.

Yield: 85%
¹ H-NMR (CDCl ₃ , 300 MHz, TMS, rt δ / ppm) 3.1 (s, 6H), 6.7 (d, 2H), 7.7 (d, 2H), 9.8 (s, 1H)
ESI-TOFMS (+) [M + Na] ⁺ = 172

Determination of Toluene A solution containing p-dimethylaminobenzaldehyde as a reagent produced in Example 1, toluene as a measurement target, piperidine as an additive, and formaldehyde as an interfering substance in ethanol was prepared. The final concentration of p-dimethylaminobenzaldehyde in the solution was 6.0 mM, the final concentration of toluene was 0 to 3.0 mM, the final concentration of piperidine was 3.0 mM, and the final concentration of formaldehyde was 1.5 mM. The solution was prepared by mixing a reagent solution containing reagents and additives in ethanol and a test sample containing toluene and formaldehyde in ethanol.

  After preparing the above solution, it was kept at room temperature for 30 minutes. Thereafter, the sample was diluted 300 times, and first, an absorption spectrum was measured. The results are shown in FIG. The curves are the results when the toluene concentration is 0, 0.1, 0.6, 1.2, and 3.0 mM in order from the bottom. As the toluene concentration increases, the peak at a wavelength of 455 nm increases, and when the toluene concentration is 0 (that is, the dye) It can be seen that the absorbance at 455 nm is almost zero. Therefore, in this example, it can be seen that toluene can be quantified with the highest sensitivity by measuring the absorbance at a wavelength of 455 nm. Therefore, the horizontal axis represents the toluene concentration, and the vertical axis represents the absorbance at a wavelength of 455 nm.

  The results are shown in FIG. As shown in FIG. 2, despite the presence of formaldehyde, a high linear relationship was obtained between the toluene concentration and the absorbance, indicating that the toluene concentration can be accurately measured with the reagent of the present invention.

In the Example of this invention, the absorption spectrum of the mixed solution of the reagent of this invention and various concentrations of toluene is shown. It is a figure which shows the relationship between toluene concentration at the time of measuring toluene of various density | concentration in the Example of this invention, and a light absorbency.

Claims (4)

A reagent for measuring toluene and / or xylene containing a compound having a structure represented by the following general formula [I] as an active ingredient.

(However, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and the alkyl group includes one or more carboxyl groups, hydroxyl groups, and amino groups. , Halogen, sulfonyl group and / or thiol group, R ₃ , R ₄ , R ₅ and R ₆ are independently of each other a hydrogen atom, a linear or branched group having 1 to 10 carbon atoms Type alkyl group (the alkyl group may be substituted with one or more carboxyl group, hydroxyl group, amino group, halogen, sulfonyl group and / or thiol group), amino group, nitro group, halogen, carboxyl Represents a group, a hydroxyl group, a sulfonyl group or a thiol group.) The reagent according to claim _1, wherein, in the general formula [I], R ₁ and R ₂ are each independently a methyl group or an ethyl group. The reagent according to claim 1 or 2, wherein, in the general formula [I], R ₃ , R ₄ , R ₅ and R ₆ are hydrogen atoms. A method for measuring toluene and / or xylene, comprising: bringing the reagent according to any one of claims 1 to 3 into contact with a test sample and measuring the produced dye.

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