JP3873058B2 - Carbonyl compound trapping material and method for quantifying carbonyl compound using the material - Google Patents

Description

  The present invention relates to a carbonyl compound-collecting material used for collecting carbonyl compounds of aldehydes and ketones, and a carbonyl compound quantification method using the material.

In recent years, the environmental effects of carbonyl compounds of aldehydes such as formaldehyde and acetaldehyde and ketones such as acetone and acrolein in water and air have become a social problem. For example, the influence on the living environment and the working environment caused by carbonyl compounds released from building materials and furniture accompanying the airtightness of houses has become a social problem. In order to examine measures against such problems, it is first necessary to measure the amount of carbonyl compounds in the atmosphere. Therefore, it is desirable to develop a method that can easily measure the amount of carbonyl compounds in the room and other atmospheres. ing.
As a quantification method for carbonyl compounds, a carbonyl compound trapping material in which silica gel is impregnated with 2,4-dinitrophenylhydrazine (hereinafter sometimes referred to as DNPH) together with phosphoric acid is a standard quantification method. Widely used (Non-Patent Documents 1 and 2).
As a quantitative method using a compound other than hydrazine, silica gel is impregnated with O- (2,3,4,5,6-pentafluorobenzyl) hydroxyamine (hereinafter sometimes referred to as PFBOA) and phosphoric acid. A quantitative method using a trapped carbonyl compound collector has been reported (Non-patent Document 3).
Recently, a method for quantifying a low-concentration carbonyl compound in automobile exhaust gas has been tried, and a method of sampling the exhaust gas at a high temperature (about 80 ° C.) has been used (Non-patent Document 2).

Waters High Performance Liquid Chromatography Column / Consumables Catalog 2002, Atmospheric Sepp Pack ~ DNPH / Ozone Scrubber ~ Page 20, Nippon Waters Co., Ltd. 2001 Chromatography product catalog, pages 78-80, Sigma-Aldrich Japan Co., Ltd., August 2001 Yasuaki Mori et al., Environmental Chemistry, Volume 7, 515-520 (1997)

However, as a result of the study by the present inventors, a collection material containing hydrazine such as DNPH is extremely excellent in reactivity with a carbonyl compound, so that a low concentration carbonyl compound can be quantified, but at the time of production of the collection material. Even before measurement, it reacts with a trace amount of carbonyl compounds present in the atmosphere or indoor air, and the blank value before measurement varies. It has been found that there is a problem that it is difficult to accurately measure the compound. Therefore, in order to reduce the variation of the blank value before the measurement, when the collection material was washed with acetonitrile before adsorbing the carbonyl compound, it was clear that DNPH was eluted from the silica gel with the acetonitrile washing. Became.
Furthermore, when the present inventors sampled an air sample in a general residential environment of about 25 to 30 ° C. using the above-mentioned collection material containing PFBOA instead of DNPH, compared with the collection material containing DNPH. Only about 70 to 77% of formaldehyde can be collected, and at high temperatures such as in summer, the carbonyl compound may not be sufficiently collected even if a carbonyl compound collecting material containing PFBOA is used. It was revealed.
The object of the present invention is to eliminate the influence of low-concentration carbonyl compounds that react before measurement, thereby reducing variation in measured values, and to accurately quantify low-concentration aldehydes and ketones during measurement. Another object of the present invention is to provide a carbonyl compound collector capable of quantifying a carbonyl compound at a concentration lower than or equal to that of a collector containing DNPH, which is standard even at high temperatures.

  The present invention is a carbonyl compound collector comprising a benzylhydroxyamine compound represented by formula (1), a mineral acid, and an adsorbent (A).

A: At least one adsorbent selected from the group consisting of silica gel, alumina, cellulose, and activated carbon, and does not contain a cation exchange group.

[式中、Ｒは、アルコキシ基、ハロアルコキシ基、ニトロ基又はシアノ基を表し、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子又はアルキル基を表す。芳香族基の水素原子は、アルキル基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリール基、ニトロ基、又はシアノ基で置換されていてもよい。]

[Wherein, R represents an alkoxy group, a haloalkoxy group, a nitro group or a cyano group, and R ¹ and R ² each independently represents a hydrogen atom or an alkyl group. The hydrogen atom of the aromatic group may be substituted with an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an aryl group, a nitro group, or a cyano group. ]

Before using the carbonyl compound collector of the present invention, the carbonyl compound collector of the present invention is washed with a hydrophilic solvent such as acetonitrile. The unreacted carbonyl compound trapping material can accurately quantify low-concentration carbonyl compounds. That is, the carbonyl compound trapping material of the present invention can be quantified more accurately for air samples containing a low concentration of carbonyl compound to the same extent as the trapping material containing DNPH, especially formaldehyde and acetaldehyde. it can. And it can quantify accurately also about compounds, such as a low concentration acrolein and acetone.
In addition, when a benzylhydroxyamine compound having a cyano group is used as a carbonyl compound trapping material, it reacts with low concentrations of aldehydes and ketones to form a derivative that can be detected by liquid chromatography. Become.
Furthermore, in the measurement of automobile exhaust gas, a method of sampling high temperature gas for 10 minutes is used, and the derivative collected by the collection material of the present invention is stable in the collection tube even at a high temperature of about 80 ° C. Can be used even at high temperatures.

Hereinafter, the present invention will be described in detail.
The adsorbent used in the present invention is at least one adsorbent selected from the group consisting of silica gel, alumina, cellulose and activated carbon.
As the silica gel, a particulate or powdery silica gel whose main component is a particle size of about 10 to 500 μm, preferably about 40 to 300 μm is usually used. Specifically, commercially available silica gels for chromatography such as silica gel manufactured by Kanto Chemical Co., Inc., silica gel manufactured by Fuji Silysia Chemical Co., Ltd., silica gel manufactured by Merck Co., Ltd., silica gel manufactured by Sigma Aldrich Co., etc. are used. Among these, silica gel adjusted to neutral is preferable.
As alumina, particulate activated alumina is usually used. Specifically, commercially available activated aluminas for chromatographs such as aluminum oxide 90 activated basic manufactured by Merck & Co., Ltd., activated alumina A11 and AC-11 manufactured by Sumitomo Chemical Co., Ltd. are exemplified.
As the cellulose, particulate or powdery cellulose is usually used, and specific examples include KC floc (manufactured by Sanyo Kokusaku Pulp Co., Ltd.).
As the activated carbon, particulate activated carbon and powder activated carbon are used, and activated carbon for a catalyst carrier is preferably used.
Moreover, different adsorbents may be used in combination as the adsorbent, for example, activated carbon mixed silica gel or the like may be used.

The adsorbent used in the present invention does not contain cation exchange groups such as sulfonic acid groups, carboxyl groups, and phosphoric acid groups. That is, the adsorbent is different from an adsorbent containing a cation exchange group such as silica gel into which a benzenesulfonic acid group is introduced, carboxyl methyl cellulose, cellulose into which a sulfoethyl group is introduced.
In addition, a carbonyl compound trapping material using an adsorbent that does not contain a cation exchange group tends to be more excellent in trace analysis of carbonyl compounds such as acetaldehyde, acrolein, and acetone.

R in the benzylhydroxyamine compound (1) used in the present invention is an alkyl group having about 1 to 8 carbon atoms such as a methyl group or an ethyl group, preferably about 1 to 4 carbon atoms; such as a methoxy group or an ethoxy group. An alkoxy group having about 1 to 4 carbon atoms; a haloalkyl group composed of a halogen atom such as chlorine or fluorine such as a trifluoromethyl group and an alkyl group having about 1 to 4 carbon atoms: about 1 to 4 carbon atoms such as a trifluoromethoxy group A nitroalkoxy group; a nitro group or a cyano group.
The hydrogen atom of the aromatic group in the benzylhydroxyamine compound (1) is an alkyl group having about 1 to 8 carbon atoms, preferably about 1 to 4 carbon atoms; a halogen atom such as chlorine or fluorine, and 1 to 1 carbon atoms. A haloalkyl group composed of about 4 alkyl groups: an alkoxy group having about 1 to 4 carbon atoms; an aryl group to which an alkyl group having about 6 to 10 carbon atoms may be further bonded; a nitro group; or a cyano group. It may be.
R ¹ and R ² in the benzylhydroxyamine compound (1) each independently represent a hydrogen atom or an alkyl group having about 1 to 8 carbon atoms, and among them, a hydrogen atom is preferable.

  Examples of the benzylhydroxyamine compound (1) include O- (4-nitrobenzyl) hydroxylamine, O- (4-methoxybenzyl) hydroxylamine, O- (4-ethoxybenzyl) hydroxylamine, O- (2 , 5-dimethylbenzyl) hydroxylamine, O- (2,4-dimethoxybenzyl) hydroxylamine, O- (3,4-dimethoxybenzyl) hydroxylamine, O- (2,4,5-trimethoxybenzyl) hydroxylbenzyl Amine, O- (3,4,5-trimethoxybenzyl) hydroxylamine, O- (2-trifluoromethylbenzyl) hydroxylamine, O- (3-trifluoromethylbenzyl) hydroxylamine, O- (4-tri Fluoromethylbenzyl) hydroxylamine, O- (2 Trifluoromethoxybenzyl) hydroxylamine, O- (3-trifluoromethoxybenzyl) hydroxylamine, O- (4-trifluoromethoxybenzyl) hydroxylamine, O- [3,5-bis (trifluoromethyl) benzyl] hydroxyl An amine, a compound having a cyano group represented by formula (2),

［式中、Ｒ^１およびＲ^２は前記と同じ意味を表し、Ｒ’は炭素数１〜４程度のアルキル基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、ニトロ基又はシアノ基を表す。芳香族基の水素原子は、アルキル基、ハロアルキル基、アルコキシ基、ハロアルコキシ基、アリール基、ニトロ基、又はシアノ基で置換されていてもよい。］
などが挙げられる。
中でも、シアノ基を有する化合物（２）が、後述するように液体クロマトグラフで検出可能な誘導体（３）を与えることから好ましく、具体的には、Ｏ−（４−シアノベンジル）、Ｏ−（４−シアノ−２−ニトロベンジル）ヒドロキシルアミン、Ｏ−（４−シアノ−２−メトキシベンジル）ヒドロキシルアミン、Ｏ−（４−シアノ−２−エトキシベンジル）ヒドロキシルアミン、Ｏ−（４−シアノ−２−イソプロポキシベンジル）ヒドロキシルアミンなどが例示され、シアノ基を有する化合物（２）の中でもＲ’がアルコキシ基である化合物が好ましく、とりわけ、Ｏ−(４−シアノ−２−メトキシベンジル)ヒドロキシアミン、Ｏ−(４−シアノ−２−エトキシベンジル)ヒドロキシアミンが好適である。

[Wherein, R ¹ and R ² represent the same meaning as described above, and R ′ represents an alkyl group having about 1 to 4 carbon atoms, a haloalkyl group, an alkoxy group, a haloalkoxy group, a nitro group, or a cyano group. The hydrogen atom of the aromatic group may be substituted with an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an aryl group, a nitro group, or a cyano group. ]
Etc.
Among them, the compound (2) having a cyano group is preferable because it gives a derivative (3) that can be detected by liquid chromatography as described later. Specifically, O- (4-cyanobenzyl), O- ( 4-cyano-2-nitrobenzyl) hydroxylamine, O- (4-cyano-2-methoxybenzyl) hydroxylamine, O- (4-cyano-2-ethoxybenzyl) hydroxylamine, O- (4-cyano-2) -Isopropoxybenzyl) hydroxylamine and the like, and among the compounds (2) having a cyano group, a compound in which R 'is an alkoxy group is preferable, and in particular, O- (4-cyano-2-methoxybenzyl) hydroxyamine, O- (4-cyano-2-ethoxybenzyl) hydroxyamine is preferred.

Taking O- (4-cyano-2-ethoxybenzyl) hydroxyamine as an example for the production method of benzylhydroxyamine compound (1), the corresponding alkoxy group is introduced from cyanotoluene as shown in the following reaction formula. A method of synthesizing via easy cyanocresol (14) and the like can be mentioned.
Further, a mineral acid salt obtained by further reacting a mineral acid with formula (18) (for example, formula (19) represents a hydrochloride of O- (4-cyano-2-ethoxybenzyl) hydroxyamine). When used, it can be easily purified by recrystallization. Accordingly, rather than immediately using the benzylhydroxyamine compound (1) as represented by the formula (18), it is purified as a mineral acid salt of the benzylhydroxyamine compound (1) and then neutralized with aqueous ammonia. Therefore, the method used as the benzylhydroxyamine compound (1) is recommended.

The benzylhydroxyamine compound (1) is usually mixed with a hydrophilic solvent and used as a solution having a concentration of the compound (1) of 1 to 30 wt% because of easy handling. If the solution is 1 wt% or more, it is preferable because the mixing tends to be easy, and if it is 30 wt% or less, the solubility of the compound (1) tends to be excellent.
Here, examples of the hydrophilic solvent include lower aliphatic nitriles, lower alcohols, lower aliphatic ethers, and lower cyclic ethers. In the present specification, a lower aliphatic nitrile is an aliphatic nitrile having about 6 or less carbon atoms such as acetonitrile, and a lower alcohol is an alcohol having about 5 or less carbon atoms such as methyl alcohol or ethyl alcohol. Ether means an aliphatic ether having about 10 or less carbon atoms, and lower cyclic ether means a cyclic ether having about 6 or less carbon atoms such as tetrahydrofuran. Among these hydrophilic solvents, acetonitrile, methyl alcohol and the like are preferable, and acetonitrile is particularly preferable.
The amount of the benzylhydroxyamine compound (1) used is usually about 0.01 to 5 parts by weight, preferably about 0.2 to 2.5 parts by weight, with respect to 100 parts by weight of the adsorbent. The amount of 0.01 part by weight or more is preferable because the carbonyl compound tends to be sufficiently collected, and the amount of 5 parts by weight or less is preferable because the blank value tends to be kept low.

Examples of the mineral acid used in the present invention include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc. Among them, the carbonyl compound collecting material using phosphoric acid tends to be excellent in storage stability, reactivity, and collecting efficiency. From the above, phosphoric acid is preferred as the mineral acid.
As the usage-amount of a mineral acid, it is about 2-50 mol normally with respect to 1 mol of benzylhydroxyamine type compounds (1), Preferably it is about 5-20 mol. When the amount is 2 mol or more, it is preferable because the benzylhydroxyamine compound (1) can be sufficiently converted to a salt of a mineral acid, and when the amount is 50 mol or less, corrosion of the adsorbent tends to be reduced. Therefore, it is preferable.
A mineral acid is usually used as a solution in which an aqueous solution of a mineral acid is mixed with a hydrophilic solvent because of easy handling. Specifically, phosphoric acid will be described as an example. A hydrophilic solvent may be mixed in a phosphoric acid aqueous solution of about 50 to 90 wt% to prepare a 5 to 20 wt% solution. It is preferable to handle a mineral acid aqueous solution as a high-concentration mineral acid aqueous solution in an easy-to-handle range because impurities such as formaldehyde and acetaldehyde derived from water tend to be reduced.

  The carbonyl compound trapping material of the present invention contains the benzylhydroxyamine compound (1), mineral acid and the adsorbent. As a method for producing a carbonyl compound collector, for example, (a) a solution of the compound (1) is mixed with an adsorbent previously washed with a hydrophilic solvent and dried for about 0.5 to 120 minutes, preferably Is a method of stirring for about 5 to 60 minutes, followed by adding the mineral acid solution and stirring for about 0.5 to 5 hours, followed by filtration and drying. (A) After the adsorbent packed in the column or the like is washed with a hydrophilic solvent, the solution of the compound (1) is circulated to the column, and the amount of the compound (1) is reduced from the solution discharged from the column. A method in which the mineral acid solution is circulated under the same conditions after being carried out, (c) a hydrophilic solvent of the benzylhydroxyamine compound (1) and the mineral acid solution are mixed, and the benzylhydroxyamine compound (1 And the like, and a method of obtaining crystals or a solution and mixing with an adsorbent. Among them, the method (a) is preferable because a large amount of the carbonyl compound trapping material can be treated easily and in a short time.

［式中、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同じ意味を表す。］
で表される誘導体を得て、該誘導体を含むカルボニル化合物捕集材から親水性溶媒で洗浄して誘導体（３）を溶出させ、得られた誘導体（３）を含む洗浄液をキャピラリーＧＣ／ＭＳなどのガスクロマトグラフィ、液体クロマトグフィ等で分析してカルボニル化合物を定量する方法などが挙げられる。 Specifically, the carbonyl compound quantification method is illustrated by first washing the carbonyl compound collector with a hydrophilic solvent, drying it in a clean state such as under reduced pressure, and then subjecting the following carbonyl compound in an air sample or water sample to Compound R ³ C (═O) R ⁴
[Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having about 1 to 8 carbon atoms, or an alkenyl group having about 1 to 8 carbon atoms. ]
Is contacted with the carbonyl compound collector of the present invention, and the formula (3)

[Wherein, R, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above. ]
The derivative (3) is eluted from the carbonyl compound-collecting material containing the derivative by washing with a hydrophilic solvent, and the resulting washing solution containing the derivative (3) is capillary GC / MS, etc. And quantifying the carbonyl compound by gas chromatography, liquid chromatography or the like.

Here, by washing the collection material before collecting the carbonyl compound, it is possible to elute the carbonyl compound that has reacted at the time of production of the collection material. As a result, at the time of measurement, a low concentration carbonyl compound can be accurately quantified. The mineral salt of the unreacted benzylhydroxyamine compound (1) is not eluted with a hydrophilic solvent and can be used for quantification. In addition, although the said washing | cleaning and drying may be implemented immediately before a measurement, for example, when filling a collection tube with a carbonyl compound collection material, after carrying out washing and drying after manufacturing a collection tube, When used as a carbonyl compound quantification kit obtained by sealing with a non-breathable material such as an aluminum laminated bag or can, it is preferable because it is easy to handle and does not become so contaminated that variations in measured values become a problem.
The cleaning of the collection material usually uses about 5 to 20 parts by weight of a hydrophilic solvent about 1 to 2 times per 1 part by weight of the carbonyl compound collection material. With the amount and number of times as described above, a collection tube with little variation in measured values can be obtained.

Specific examples of the carbonyl compound [R ³ C (═O) R ⁴ ] that can be quantified in the present invention include formaldehyde, acetaldehyde, acetone, acrolein, butanone, valeraldehyde, benzylaldehyde, heptaldehyde and the like.

［式中、Ｒ’、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、は前記と同じ意味を表す。］ Among the derivatives (3), a compound represented by formula (4), that is, a reaction product of a compound (2) having a cyano group and a carbonyl compound represented by [R ³ C (═O) R ⁴ ] Since it is a compound having ultraviolet light absorption, it can be quantified by a liquid chromatograph equipped with a UV detector. This method is preferable because it can be analyzed in a trace amount and is a simpler analysis method. The compound represented by the formula (2) that gives the formula (4) used in the method is a carbonyl compound collector. Suitable as an active ingredient.

[Wherein, R ′, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above. ]

As a specific quantification method of the carbonyl compound [R ³ C (═O) R ⁴ ], for example, an air sample is used by using a collection tube in which a container having air permeability is filled with a carbonyl compound collection material. For example, a method of collecting the carbonyl compound from the sample and taking out the derivative (3) from the collection tube and quantifying it can be used. Specifically, a quantitative method using an active sampler as a collecting tube will be described below as a representative example. First, the collection tube, which is a tubular container having an inner diameter of 3 to 15 mm and a length of about 1 to 10 cm, is filled with a carbonyl compound collection material to such an extent that the air sample is sufficiently circulated, and the carbonyl compound collection material is held. Cap with a filter that can be used. Next, the obtained product is washed with a hydrophilic solvent and dried to prepare a carbonyl compound collecting tube. The collection tube is usually stored under seal. Next, the seal is released under an air sample atmosphere, a pump is connected, and an air sample is collected at a pump suction speed of about 0.01 to 1.5 l / min. Subsequently, the collection tube is washed with a hydrophilic solvent to obtain a solution containing the derivative (3) and the hydrophilic solvent. Finally, the solution is analyzed by liquid chromatography, gas chromatography or the like.
As described above, in addition to the quantification method using an active sampler that collects an air sample with a pump, the collection is performed by filling a carbonyl compound collection material in a container such as a porous tube that is entirely or principally breathable. An example is a method in which a tube is prepared and collected by allowing the collection tube to stand on an air sample and then quantified in the same manner, that is, a quantification method using a passive sampler.

As the gas chromatography, analysis by a capillary GC / MS method or the like is preferable because accurate analysis is possible.
In particular, when the benzylhydroxyamine compound (1) contained in the carbonyl compound-collecting material is a compound (2) having a cyano group, the derivative (4) is provided, so that it can be easily obtained by liquid chromatography equipped with a UV detector. It is preferable because it can be analyzed.
The carbonyl compound is quantified in advance by separately preparing a derivative (3) obtained by reacting a carbonyl compound and a benzylhydroxyamine compound (1), and using the above chromatography, an absolute calibration curve method, an internal standard What is necessary is just to quantify by a method.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.
<Example of production of benzylhydroxyamine compound (1)>
(Synthesis example of 4-cyano-2-nitrotoluene (12))
Fuming nitric acid (300 ml, 7.2 mol) was added to the reactor, and 4-cyanotoluene (11) (120.0 g, 1.02 mol) was added dropwise below freezing point, and the mixture was stirred as it was for 1 hour. Ice water was added to the reaction solution, and the precipitated pale yellow solid was collected by filtration. This was air-dried to obtain water-containing 4-cyano-2-nitrotoluene (12) (300 g).
¹ H-NMR (δ, ppm, CDCl ₃ )… 2.70 (3H, s), 7.52 (1H, d), 7.79 (1H, dd), 8.28 (1H, d)

(Synthesis example of 4-cyano-2-aminotoluene (13))
4-Cyano-2-nitrotoluene (12) (300 g) and ethanol were added to the reactor, 10% palladium / carbon (9.5 g) was added, and a hydrogen catalytic reduction reaction was performed at room temperature. When absorption of hydrogen ceased, palladium / carbon was removed by filtration, and then the solvent was distilled off from the filtrate to give 4-cyano-2-aminotoluene (13) (132.5 g, yield from (11) of 98. %).
¹ H-NMR (δ, ppm, CDCl ₃ )… 2.00 (3H, s), 3.81 (2H, brs), 6.89 (1H, d), 6.97 (1H, dd), 7.10 (1H, d)

(Synthesis example of 4-cyano-2-hydroxytoluene (14))
4-Cyano-2-aminotoluene (13) (132.0 g, 1.0 mol) and 6N aqueous hydrochloric acid (800 ml) were placed in the reactor, and ice-cooled sodium nitrite (76.0 g, 1.1 mol) was added. An aqueous solution dissolved in water (320 ml) was added dropwise over 1.5 hours, and the mixture was further stirred under reflux for about 20 hours. After toluene was added to the reaction solution for extraction, an aqueous sodium hydroxide solution was added to the toluene layer to make the aqueous layer alkaline. The obtained aqueous layer was acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The obtained ethyl acetate layer was washed with saturated brine, dried, and the solvent was evaporated under reduced pressure to give 4-cyano-2-hydroxytoluene (14) (91.6 g, yield 69 from (13). %).
¹ H-NMR (δ, ppm, CDCl ₃ )… 2.31 (3H, s), 6.25 (1H, s), 7.05 to 7.22 (3H, m)

(Synthesis example of 4-cyano-2-ethoxytoluene (15))
A reactor was charged with 60% sodium hydride (4.8 g, 0.12 mol) and N, N′-dimethylformamide (40 ml), and 4-cyano-2-hydroxytoluene (14) (13.3 g) in an ice bath. , 0.1 mol) in N, N′-dimethylformamide (40 ml) was added dropwise and stirred at room temperature for 1.0 hour. Subsequently, ethyl iodide (18.7 g, 0.12 mol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 1.5 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with saturated brine, dried and evaporated under reduced pressure to give 4-cyano-2-ethoxytoluene (15) (16.1 g, (14 99%).
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.45 (3H, t), 2.26 (3H, s), 4.04 (2H, q), 7.00 (1H, s), 7.14 (1H, d), 7.19 ( 1H, d)

(Synthesis example of 4-cyano-2-ethoxy-α-bromotoluene (16))
A reactor was charged with 4-cyano-2-ethoxytoluene (15) (16.0 g, 0.1 mol) and 1,2-dichloroethane (160 ml), and 2,2′-azobiz (isobutyronitrile) at room temperature. (800 mg) and N-bromosuccinimide (19.4 g, 0.11 mol) were added, and the mixture was stirred at 80 ° C. to 90 ° C. for 1 hour. Hexane was added to the reaction solution, and the precipitated solid was collected by filtration. The resulting filtrate was concentrated to give 4-cyano-2-ethoxy-α-bromotoluene (16) (20.3 g, 85% yield from (15)).
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.50 (3H, t), 4.12 (2H, q), 4.52 (2H, s), 7.09 (1H, d), 7.21 (1H, dd), 7.42 ( 1H, d)

(Synthesis example of 4-cyano-2-ethoxy-α-hydroxyphthalimidotoluene (17))
A reactor was charged with 4-cyano-2-ethoxy-α-bromotoluene (16) (20.2 g, 0.084 mol) and N, N′-dimethylformamide (200 ml), and N-hydroxyphthalimide (14.4 g, 0.088 mol) and anhydrous potassium carbonate (12.2 g, 0.088 mol) were added, and the mixture was stirred at about 80 ° C. for 2 hours. Water was added to the reaction solution, and the precipitated solid was collected by filtration. This was dried to obtain 4-cyano-2-ethoxy-α-hydroxyphthalimidotoluene (17) (27.0 g, 99% yield from (16)).
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.39 (3H, t), 4.02 (2H, q), 5.31 (2H, s), 7.07 (1H, s), 7.27 (1H, d), 7.65 ( 1H, d), 7.72-7.84 (4H, m)

(Synthesis example of O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18))
4-Cyano-2-ethoxy-α-hydroxyphthalimidotoluene (17) (27.0 g, 0.084 mol) and ethanol (270 ml) were charged into the reactor, and hydrazine monohydrate (4.6 g, 0.091 mol) was charged. ) And stirred at about 80 ° C. for 2 hours. The precipitated white solid was removed by filtration, and the solvent was distilled off from the obtained filtrate under reduced pressure. Next, ethyl acetate was added and the mixture was washed with a dilute aqueous sodium carbonate solution and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) (13. 4 g, 83% yield from (17)).
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.45 (3H, t), 4.06 (2H, q), 4.79 (2H, s), 5.54 (2H, brs), 7.07 (1H, d), 7.26 ( 1H, dd), 7.45 (1H, d)

<Example of production of salt of benzylhydroxyamine compound (1) and mineral acid>
(Synthesis example of O- (4-cyano-2-ethoxybenzyl) hydroxyamine hydrochloride (19))
A reactor was charged with O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) (13.4 g, 0.042 mol) and diethyl ether (260 ml), and hydrochloric acid gas was blown into the reactor, followed by stirring for 0.5 hour. . The precipitated white solid was collected by filtration, washed with diethyl ether and dried. Recrystallization from a mixed solvent of water and acetonitrile gave 71% yield of white needle-like crystals from O- (4-cyano-2-ethoxybenzyl) hydroxyamine hydrochloride (19) (11.3 g, (18). )
¹ H-NMR (δ, ppm, D ₂ O) 1.42 (3H, t), 4.17 (2H, q), 5.15 (2H, s), 7.40 (1H, d), 7.42 (1H, s), 7.53 (1H, d)

<Example of production of carbonyl compound collector containing O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18), phosphoric acid and silica gel>
The O- (4-cyano-2-ethoxybenzyl) hydroxyamine hydrochloride (19) obtained above was mixed with aqueous ammonia, extracted with diethyl ether, dried and the solvent was distilled off. An acetonitrile (20 ml) solution containing the obtained O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) (476 mg, 2.5 mmol) was obtained.
In another reactor, silica gel (100 g, 60N, manufactured by Kanto Chemical Co., Inc., neutral, spherical, 63 to 210 μm) and acetonitrile (300 ml) were charged and stirred for a while, followed by filtration to remove acetonitrile. Subsequently, another acetonitrile (200 ml) was charged into the obtained washed silica gel, the acetonitrile solution containing (18) was added dropwise, and the mixture was stirred at room temperature for 10 minutes. Next, a mixed solution of 85% phosphoric acid (3.0 g, 25.8 mmol) and acetonitrile (20 ml) was added dropwise and stirred at room temperature for 1 hour. The reaction solution was filtered to remove acetonitrile, and the filtered product was further washed with acetonitrile. The material on the filter was recovered and dried to obtain 102.2 g of a carbonyl compound trap.

<Phosphate of O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18)>
After mixing O- (4-cyano-2-ethoxybenzyl) hydroxyamine hydrochloride (19) and aqueous ammonia, the mixture was extracted with ethyl acetate, and O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18 ) (80 mg, 0.42 mmol). This was dissolved in acetonitrile (12 ml), a few drops of 85% aqueous phosphoric acid solution were added dropwise, and the resulting white solid was collected by filtration under reduced pressure. The top of the filter was washed with acetonitrile, and the one on the filter was collected and dried with a vacuum pump to obtain 60 mg of a white solid. From the following CHN elemental analysis and NMR results, O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) was mixed with phosphoric acid to obtain tris {O- (4-cyano-2- It was found to be ethoxybenzyl) hydroxyamine} phosphate.
Composition formula C ₃₀ H ₃₉ N ₆ O ₁₀ P
Theoretical value: C; 41.5%, H; 4.9%, C; 9.7% Analytical value: C; 41.2%, H; 5.1%, C; 9.6%
¹ H-NMR (δ, ppm, DMSO-d ₆ )… 1.36 (9H, t), 4.10 (6H, q), 4.66 (6H, s), 7.35 (3H, d), 7.36 (3H, s), 7.48 (3H, d)

<Example of production of carbonyl compound collecting tube>
A polyethylene container having an inner diameter of 10.5 mm and a length of 30 mm as shown in FIG. 1 was filled with the carbonyl compound-collecting material (420 mg). The container was stoppered with a polypropylene filter (pore size 50 μm) to hold the collecting material. This was washed with acetonitrile (5 ml) in a glove box under a nitrogen stream and dried with a vacuum pump at about 40 ° C. for 4 hours to obtain a carbonyl compound collecting tube. The upper and lower suction ports were sealed, and further sealed in an aluminum laminate bag.
O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) was eluted through the resulting collection tube through acetonitrile / 28% aqueous ammonia = 100/3 (10 ml) and quantified under the following conditions. It was observed that 2 mg was eluted, and an almost theoretical amount of O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) was contained in the carbonyl compound collecting tube.

<Analysis conditions>
Column: SUMPAX ODS D series
5μm 4.6mmφ × 250mm
Mobile phase: acetonitrile / water = 55/45
Flow rate: 1.0 mL / min
Measurement wavelength: 240 nm (UV)
Temperature: 40 ° C
Injection volume: 1 μl

<Production Example of Derivative (3)>
The content of the carbonyl compound in the air sample can be determined by quantifying the derivative (3) obtained by reacting the mineral acid salt of the carbonyl compound and the benzylhydroxyamine compound (1). A production example of the derivative (3) necessary for this determination will be described according to the following formula.

<Synthesis Example of (3-1a)>
O- (4-Cyano-2-ethoxybenzyl) hydroxyamine hydrochloride (19-1, 2.7 g, 0.012 mol), methanol (20 ml) and water (20 ml) were charged, 36% aqueous formaldehyde was added, Stir at room temperature for 2.0 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and washed with saturated brine. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. This was purified by silica gel column chromatography using a hexane / ethyl acetate system, and O- (4-cyano-2-ethoxybenzyl) hydroxyamine phosphorus-formaldehyde derivative (3-1a, 2.2 g, yield 96%). Got.
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.45 (3H, t), 4.06 (2H, q), 5.21 (2H, s), 6.51 (1H, q), 7.05-7.50 (3H, m)

<Synthesis Example of Derivative (3-1b)>
A derivative (mixture of syn and anti forms) (3-1b, 660 mg, 64% yield) was obtained in the same manner as in the synthesis example of the derivative (3-1a) except that acetaldehyde was used.
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.44 (3H, t), 1.86 and 1.93 (3H, d), 4.05 (2H, q), 5.13 and 5.20 (2H, s), 6.83 and 7.54 (1H , q), 7.04-7.48 (3H, m)

<Synthesis Example of (3-1c)>
A derivative (3-1c, 400 mg, yield 78%) was obtained in the same manner as in the synthesis example of the derivative (3-1a) except that acetone was used.
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.43 (3H, t), 1.89 (3H, s), 1.96 (3H, s), 4.05 (2H, q), 5.15 (2H, s), 7.04 ~ 7.43 (3H, m)

<Synthesis Example of Derivative (3-1d)>
A derivative (mixture of syn and anti forms) (3-1d, 450 mg, 89% yield) was obtained in the same manner as in the synthesis example of the derivative (3-1a) except that acrolein was used.
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.44 (3H, t), 4.05 (2H, q), 5.20 and 5.23 (2H, s), 5.55 and 5.63 (2H, d and s), 6.34 to 6.48 (1H, m), 7.04-7.45 (3H, m), 7.84 (1H, d)

<Synthesis Example of Derivative (3-1e)>
A derivative (mixture of syn and anti forms) (3-1e, 400 mg, yield 55%) was obtained in the same manner as in the synthesis example of (3-1a) except that benzaldehyde was used.
¹ H-NMR (δ, ppm, CDCl ₃ ) ... 1.46 (3H, t), 4.08 (2H, q), 5.30 and 5.35 (2H, s), 7.08 and 8.20 (1H, s), 7.23 to 7.61 (8H , m)

Example 1
<Measurement of blank value>
The carbonyl compound collection tube obtained above was eluted through acetonitrile (5 ml), and 20 μl of the resulting solution was subjected to liquid chromatography in the same manner as O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18). analyzed. Separately, the amount quantified as a blank value was determined as sample 1 by the absolute calibration curve method using the derivatives (3-1a), (3-1b) and (3-1c) as standard products. Similarly, nine different carbonyl compound collecting tubes were similarly quantified (samples 2 to 10), and the results are shown in Table 1 together with sample 1.
Note that the coefficient of variation is a measure (in%) that evaluates the degree of substantial data variation by dividing the standard deviation by the average value. The smaller the coefficient of variation, the smaller the variation in the measured value. .
Table 1 shows the measurement results, and FIG. 2 (1) shows a typical chart of Table 1. For reference, (2) in FIG. 2 contains each derivative of O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) containing 0.5 μg / ml as the concentration of formaldehyde, acetaldehyde, acetone and acrolein. A chart of the sample is shown.

Samples 1 to 10 did not show peaks of derivatives of carbonyl compounds other than formaldehyde, acetaldehyde and acetone. It was also found that the blank values for formaldehyde and acetaldehyde were low and the variation was small. Acetone was higher than formaldehyde and acetaldehyde, but was found to have little variation.
(Comparative Example 1)
<Blank value of DNPH collection tube>
Ten blank values of a DNPH sampler short body (including a water formaldehyde collector, 2,4-dinitrophenylhydrazine (DNPH)) were quantified in the same manner as in Example 1. In addition, since the DNPH-formaldehyde derivative, the DNPH-acetaldehyde derivative, and the DNPH-acetone derivative are commercially available from Sigma-Aldrich, they were used. The results are shown in Table 2, and a typical chart of Table 2 is shown in FIG. For reference, FIG. 3 (3) shows a chart of a sample containing each derivative of DNPH contained at a concentration of formaldehyde, acetaldehyde and acetone of 0.5 μg / ml.

  In the case of a collection material containing DNPH, the blank values of formaldehyde and acetaldehyde are 15 times higher than the collection tube of Example 1, and the coefficient of variation is also large. Also, from the comparison of the blank charts of FIG. 2 and FIG. 3, it can be seen that the carbonyl compound trapping material of the present invention has fewer detected blank peaks than the trapping material containing DNPH.

(Example 2)
<Collection test with formaldehyde standard gas>
Air samples 1 to 6 were prepared by diluting formaldehyde generated by thermally decomposing paraformaldehyde using a standard gas generator manufactured by Gastec Co., Ltd. at a constant flow rate from a high purity air cylinder and adjusting the gas concentration to about 20 to 350 ppb. Prepared. Two carbonyl compound collection tubes were connected, and the air sample was collected at a rate of 500 ml / min for 30 minutes. After collection, formaldehyde derivative was eluted through each collection tube through acetonitrile (5 ml), and the resulting solution was quantified in the same manner as in Example 1.
The results of air samples 1 to 6 are shown in Table 3.

１）ウォーターズ社製のＤＮＰＨサンプラーにより定量したホルムアルデヒド濃度
２）発生させた濃度を１００とした時、サンプラーの１段目と２段目の合計値の反応収率

表３のホルムアルデヒド捕集試験結果から１段目にすべてのアルデヒドが捕集され、低濃度の２０ｐｐｂ付近から高濃度の３５０ｐｐｂ付近まで良好な結果を得た。

1) Formaldehyde concentration determined by DNPH sampler manufactured by Waters 2) When the generated concentration is 100, the reaction yield of the total value of the first and second stages of the sampler

From the formaldehyde collection test results in Table 3, all aldehydes were collected in the first stage, and good results were obtained from a low concentration of around 20 ppb to a high concentration of around 350 ppb.

(Example 3)
<Heat resistance test of formaldehyde derivatives>
Collection in which about 1 μg of O- (4-cyano-2-ethoxybenzyl) hydroxyamine-formaldehyde derivative (3-1a) was injected into the collection tube as the amount of formaldehyde in the carbonyl compound collection tube used in Example 1 Seven tubes were prepared, and one (time 0 min) was used to elute the derivative (3) in the same manner as in Example 1 to determine the amount collected as formaldehyde. The other collection tube was allowed to stand in a high-temperature bath at 80 ° C. for the time shown in Table 4, and the amount of the derivative was quantified. Table 4 shows the results of quantification of the derivatives in terms of formaldehyde.
From the results in Table 4, since all of the carbonyl compound collection tubes collected derivatives equivalent to about 1 μg as formaldehyde, the carbonyl compound collection material of the present invention was at least at 80 ° C. for 90 minutes. It was found that carbonyl compounds can be collected stably.

Example 4
<Measurement of formaldehyde in air samples in general residential environment>
Using the carbonyl compound collection tube obtained in Example 1, the indoor air of the actual three general residences was collected at about 25 ° C. for 30 minutes at a collection flow rate of 500 ml / min. Quantified. The results are shown in Table 5 together with the case where a DNPH sampler short body (manufactured by Waters) was used as the collection tube.
As apparent from Table 5, the carbonyl compound trapping material of the present invention is almost the same as the trapping material containing DNPH, which is a standard, even for an air sample such as indoor air in a general residence where various gases are present. Equivalent measured concentration is shown.

(Comparative Example 2)
<Measurement of formaldehyde in an air sample in a general residential environment using a carbonyl compound collector containing PFBOA>
A collection tube in which 2.5 mg of O- (2,3,4,5,6-pentafluorobenzyl) hydroxyamine (PFBOA) (manufactured by Hayashi Junyaku Kogyo Co., Ltd.) is coated on Bond Elute Junior SCX (manufactured by Varian) Created and collected indoor air in three actual general residences different from Example 4 at a temperature of about 25-30 ° C. for 30 minutes at a collection flow rate of 330 ml / min, and after elution by GC / MS (SIM) Quantified. The results are shown in Table 6 together with the case where a DNPH sampler short body (Waters) was used as the collection tube.
According to Table 6, at 25 to 30 ° C., it was revealed that the collection efficiency of PFBOA is only 70 to 77% as compared with the collection tube containing DNPH.

In addition, the derivative | guide_body made from Hayashi Junyaku Kogyo is used for the derivative | guide_body of PFBOA and formaldehyde, and conditions of GC / MS (SIM) are as follows.
<GC / MS measurement conditions>
Model HP6890 / 5972A gas chromatograph mass spectrometer Column J & W DB-1 (0.25 μm) 0.25 mmφ × 30 m
Injection temperature 250 ℃
Detector temperature 280 ℃
Column 50 ° C (10 minutes) → (10 ° C / minute) → 250 ° C (0 minutes)
Split Rate 1/30
Carrier gas He 1.0mL / min
Measurement mode SIM method Measurement mass number (m / z) formaldehyde 181
Injection volume 1 μl is injected

(Example 5)
<Collection test using passive sampler>
After filling a porous cylindrical tube (diameter 7 mm, length 40 mm) with the carbonyl compound trapping material (300 mg) of Example 1 to obtain a porous cylindrical tube passive, it is covered with an aluminum laminate and contacted with outside air. avoided. Next, 0.5 ml of a commercially available 36% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a glass container for thin layer chromatography (vertical × horizontal × height = 20 × 8 × 21 cm) and sealed for a while.
After 2 hours, put the above porous cylindrical tube type passive, seal it and leave it for 4 hours, then put out the entire volume of the porous cylindrical tube type passive filling into the glass screw tube and add acetonitrile (5 ml). And stirred for a while. The supernatant was analyzed by liquid chromatography as in Example 1. As a result, 176.6 μg of formaldehyde was collected in three average values.

  By using the carbonyl compound trapping material of the present invention, it can be used in space samples in houses, buildings, factories, waste disposal sites, etc., in air samples such as automobile exhaust gas, water and sewers, rivers Trace amounts of aldehydes such as formaldehyde and acetaldehyde and ketones such as acetone and acrolein contained in liquid samples such as seawater and industrial wastewater can be analyzed.

Carbonyl compound collecting tube used in Examples of the present invention (1): O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) and a chart of an eluate from a carbonyl compound collecting material containing a salt made of phosphoric acid and silica gel; and (2): a sample. Chart of each derivative of O- (4-cyano-2-ethoxybenzyl) hydroxyamine (18) containing 0.5 μg / ml as the concentration of formaldehyde, acetaldehyde, acetone and acrolein (1): DNPH sampler short body (waters formaldehyde collector, including 2,4-dinitrophenylhydrazine (DNPH)) and (3): concentration of formaldehyde, acetaldehyde and acetone in the sample Chart of DNPH derivatives contained at 0.5 μg / ml

Explanation of symbols

1: Carbonyl compound collecting tube 2: Container (made of polyethylene)
3: Carbonyl compound collector 4: Polypropylene filter 5: Suction port 11: Formaldehyde 12: Acetaldehyde 13: Acetone 14: Acrolein 15: O- (4-cyano-2-ethoxybenzyl) hydroxyamine
16: 2,4-dinitrophenylhydrazine (DNPH)
(1): Blank chart (chart when nothing is collected)
(2): O- (4-cyano-2-ethoxybenzyl) contained in the sample as a concentration of formaldehyde, acetaldehyde, acetone and acrolein of 0.5 μg / ml
Chart (3) of each derivative of hydroxyamine (18): 0.5% concentration of formaldehyde, acetaldehyde and acetone in the sample
Chart of each derivative of 2,4-dinitrophenylhydrazine (DNPH) contained in μg / ml

Claims (7)

A carbonyl compound collector comprising a benzylhydroxyamine compound represented by formula (1), a mineral acid, and an adsorbent (A).
A: At least one adsorbent selected from the group consisting of silica gel, alumina, cellulose, and activated carbon, and does not contain a cation exchange group.

[Wherein, R represents an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a nitro group or a cyano group, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. The hydrogen atom of the aromatic group may be substituted with an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an aryl group, a nitro group, or a cyano group. ] The carbonyl compound trapping material according to claim 1, wherein the formula (1) is a benzylhydroxyamine compound represented by the formula (2).

[Wherein, R ¹ and R ² represent the same meaning as described above, and R ′ represents an alkyl group having 1 to 4 carbon atoms, a haloalkyl group, an alkoxy group, a haloalkoxy group, a nitro group, or a cyano group. The hydrogen atom of the aromatic group may be substituted with an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an aryl group, a nitro group, or a cyano group. ]   The carbonyl compound collector according to claim 1 or 2, wherein the mineral acid is phosphoric acid.   The adsorbent (A) is silica gel for chromatography, The carbonyl compound trapping material according to any one of claims 1 to 3.   The collection tube formed by filling the container which has air permeability with the carbonyl compound collection material in any one of Claims 1-4. The trapping material according to claim 3 or 4 is washed with at least one hydrophilic solvent selected from the group consisting of lower aliphatic nitriles, lower alcohols, lower aliphatic ethers and lower cyclic ethers, and then dried. In the collected material,
R ³ C (═O) R ⁴
[Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 1 to 8 carbon atoms. ]
The carbonyl compound is adsorbed as a derivative represented by the formula (3) by passing through a sample containing the carbonyl compound represented by the formula (3), and subsequently washed with a hydrophilic solvent. A method for quantifying a carbonyl compound, characterized by quantifying.

[Wherein, R, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above. ]   A carbonyl compound determination kit comprising the collection tube according to claim 5 sealed with a non-breathable material.

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