JP5116245B2 - Calibration curve compound for use in automated analyzers - Google Patents
Calibration curve compound for use in automated analyzers Download PDFInfo
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- JP5116245B2 JP5116245B2 JP2006083377A JP2006083377A JP5116245B2 JP 5116245 B2 JP5116245 B2 JP 5116245B2 JP 2006083377 A JP2006083377 A JP 2006083377A JP 2006083377 A JP2006083377 A JP 2006083377A JP 5116245 B2 JP5116245 B2 JP 5116245B2
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- 0 **(*c(ccc(Br)c1)c1[Tl])c(cc1)cc(Cl)c1F Chemical compound **(*c(ccc(Br)c1)c1[Tl])c(cc1)cc(Cl)c1F 0.000 description 1
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本発明は検量線作成用化合物に係り、特に試料中の微量ハロゲンおよび硫黄を迅速に高精度で自動定量分析する際の検量線作成用の新規化合物に関する。 The present invention relates to a compound for preparing a calibration curve, and more particularly to a novel compound for preparing a calibration curve when a trace amount of halogen and sulfur in a sample is rapidly and automatically analyzed quantitatively.
環境問題への意識の高まりから、廃棄物や土壌等の安全性に関心が寄せられており、それらに含有されている元素の中、分析頻度の高いハロゲンおよび硫黄を同時に定量分析する手法が求められている。たとえば、廃棄物固形燃料（ＲＤＦ）では、廃フィルム系よりも古紙系のものに臭素をはじめとするハロゲンが多く含まれている。また、廃食油から再生した燃料にはハロゲンや硫黄が全く含まれていないが重油には硫黄分が多く含まれている。着色プラスチック材料（ＰＰ：ポリプロビレン）には青色の顔料の成分に由来すると考えられるフッ素が含まれている。乾燥土壌（ピート）中は、産地が北海道の火山地域のため火山に由来するものと考えられる硫黄およびフッ素が含まれている。その他飼料添加物や防カビ剤および防菌材にはヨウ素が含まれている。 Due to the growing awareness of environmental issues, there is an increasing interest in the safety of waste and soil, and a method for simultaneous quantitative analysis of halogens and sulfur, which are frequently analyzed, is required. It has been. For example, solid waste fuel (RDF) contains more halogens such as bromine in waste paper than waste film. In addition, fuel regenerated from waste cooking oil does not contain any halogen or sulfur, but heavy oil contains a large amount of sulfur. The colored plastic material (PP: polypropylene) contains fluorine which is considered to be derived from the component of the blue pigment. The dry soil (peet) contains sulfur and fluorine, which are thought to be derived from volcanoes, because the production area is Hokkaido's volcanic area. Other feed additives, fungicides and fungicides contain iodine.
従来の検量線作成標準化合物では、１元素ごとに検量線を作成しなければならず、これらの元素を自動分析するための装置としては種々のものが開発されているが、ハロゲンと硫黄を一括自動分析できる装置に使用する検量線作成用の化合物の合成と標準分析法は未だ一般的に確立されておらず、従来の検量線作成用の標準化合物では、各元素の分析ごとに夫々検量線を作成しなければならず、試料中に各種ハロゲンや硫黄が分析対象として含まれている環境資源・材料などの自動分析には夫々の検量線の作成のために相当な時間を要していた。 In the conventional calibration curve preparation standard compound, a calibration curve must be prepared for each element, and various devices have been developed for automatic analysis of these elements. The synthesis and standard analysis method of the calibration curve preparation compound used for the equipment that can be automatically analyzed has not been generally established yet, and the conventional standard curve creation standard compound has a calibration curve for each element analysis. The automatic analysis of environmental resources and materials that contain various halogens and sulfur in the sample as analysis targets required considerable time to create each calibration curve. .
本発明者等は多種類のハロゲンと硫黄を含み、微量ハロゲン・硫黄自動分析装置用の検量線作成用化合物として利用出来る化合物の合成をすでに試みているが（非特許文献１）、主要な４種の４ハロゲン（Ｆ、Ｃｌ、Ｂｒ、Ｉ）の全てと硫黄（Ｓ）を含む化合物については、その合成に収率や出発原料の選択等に種々の困難を伴い、そのような化合物およびその製造方法自体は未だ知られていない。本発明者等はハロゲン化アニリン化合物とハロゲン化ベンゼンスルホニル化合物の縮合によるかゝる化合物の合成に成功した。この化合物については検量線作成用化合物としての機能を果たすことが確認され、これを用いて、廃棄物等の各種環境試料の定量分析を行なったところ、これが検量線作成用化合物として有用であることが実証され、本発明を完成するに到った。
本発明は２−ヨウ化−４−臭化ーアニリンと３−塩化−４−フッ化ベンゼンスルホニルクロリドの縮合反応によって得られる下記構造式を有する化合物
The present invention is a compound having the following structural formula obtained by condensation reaction of 2-iodo-4-bromide-aniline and 3-chloro-4-fluorobenzenesulfonyl chloride.
前記形式の縮合反応は一般に塩基性で進行するものとされているが、本発明においてハロゲン化アニリン化合物とハロゲン化ベンゼンスルホニル化合物の縮合反応を実施する際には溶媒の選択が極めて重要である。すなわち、無機塩基を溶媒として用いた場合には反応はほとんどの場合実質的に進行せず、また種々の有機溶媒についても夫々の得失があり、ピリジンを用いることがもっとも好ましい結果を与えることが判明した。 In general, the condensation reaction of the above type is considered to proceed in a basic manner, but in the present invention, the selection of the solvent is extremely important when the condensation reaction of the halogenated aniline compound and the halogenated benzenesulfonyl compound is carried out. That is, when an inorganic base is used as a solvent, the reaction does not proceed substantially in most cases, and there are advantages and disadvantages with respect to various organic solvents, and it turns out that the use of pyridine gives the most preferable result. did.
前記縮合反応は低温では反応が実質的に生起せず、また高温になるほど反応速度は増大するが、副反応が生じやすくなり目的化合物の収率や純度が低下する。出発原料であるハロゲン化ーアニリンとハロゲン化ベンゼンスルホニル化合物とを氷冷下で混合した後室温で反応させることが最も好ましい。 The condensation reaction does not substantially occur at low temperatures, and the reaction rate increases as the temperature increases, but side reactions tend to occur and the yield and purity of the target compound decrease. Most preferably, the starting material halogenated aniline and the halogenated benzenesulfonyl compound are mixed under ice cooling and then reacted at room temperature.
このようにして得られたＮ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミド（１）は赤外線分光（ＩＲ）分析、核磁気共鳴（ＮＭＲ）分析および融点測定によってその前記構造式との一致や物性等が確認された。さらにＮ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドを用いて作成した検量線はその相関係数において直線性が極めて高く、また市販の標準物質を元素分析した際の結果は許容される誤差範囲内にあり、この化合物を検量線作成用化合物として使用できることが確認された。また前記化合物を用いて実際の試料を分析した際にも標準物質を用いた場合と比較して精度がほとんど変わりのないことが判明した。
The N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorinated benzenesulfonamide (1) thus obtained was analyzed by infrared spectroscopy (IR) analysis, nuclear magnetic resonance ( NMR) analysis and melting point measurement confirmed the agreement with the structural formula, physical properties, and the like. Further, a calibration curve prepared using N- (2′-iodinated-4′-phenyl bromide) -3-chloride-4-fluorinated benzenesulfonamide has extremely high linearity in its correlation coefficient, and is commercially available. The results of the elemental analysis of the reference material were within an allowable error range, and it was confirmed that this compound can be used as a calibration curve preparing compound. Further, it was found that the accuracy was almost unchanged even when an actual sample was analyzed using the compound as compared with the case where a standard substance was used.
したがって本発明による前記化合物を検量線の作成に用いた場合、Ｆ、Ｃｌ、Ｂｒ、ＩおよびSの検量線を一回の操作で作成することができ、自動分析装置を用いて行われるこれら元素の分析についての所要時間が著しく短縮される。 Therefore, when the compound according to the present invention is used for preparing a calibration curve, calibration curves for F, Cl, Br, I and S can be created in a single operation, and these elements are performed using an automatic analyzer. The time required for analysis is significantly reduced.
実施例
Ｎ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドの合成
２−ヨウ化−４−臭化−アニリン１．００ｇ（３．３７ｍｍｏｌ）をピリジン３ｍｌに溶解し、これに対して３−塩化−４−フッ化−ベンゼンスルホニルクロリド１．００ｇ（４．４０ｍｍｏｌ）をピリジン４ｍＬに溶解した溶液を氷冷下で攪拌しながら約３０分にわたって滴下した。滴下後室温で３日間静置し、反応液を１ｍｏｌ／Ｌ塩酸溶液中に注ぎ、沈澱物を濾過し、水で洗浄した。沈澱物をカラムクロマトグラフで分離精製後、再結晶を行って精製した。白色結晶（融点１３３oC）が収率４３％で得られた。得られた目的生成物は下記ＩＲ，ＮＭＲ並びに元素分析によって前記構造式を有するＮ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドであることが示された。
IR: 3265cm-1
N-H, 1170cm-1 S=O
NMR: 6.75(1H, N-H), 7.20(1H, aromatic), 7.46〜 7.60(3H, aromatic), 7.82 (1H, aromatic), 7.85(1H,
aromatic)
元素分析値 理論値 Ｃ：29.38％ Ｈ：1.44％ Ｎ：2.86％
分析値 Ｃ：29.54％ Ｈ：1.63％ Ｎ：2.83％
Example N- (2'-Iodinated-4'-phenyl bromide) -3-Synthesis of 4-chloro-4-fluorinated benzenesulfonamide 2-iodinated-4-brominated-aniline 1.00 g (3.37 mmol) ) Is dissolved in 3 ml of pyridine, and a solution prepared by dissolving 1.00 g (4.40 mmol) of 3-chloro-4-fluorinated-benzenesulfonyl chloride in 4 mL of pyridine is stirred for about 30 minutes under ice cooling. Dripped over. After dropping, the mixture was allowed to stand at room temperature for 3 days, the reaction solution was poured into a 1 mol / L hydrochloric acid solution, and the precipitate was filtered and washed with water. The precipitate was separated and purified by column chromatography and then purified by recrystallization. White crystals (melting point 133 ° C.) were obtained with a yield of 43%. The obtained target product is N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorobenzenesulfonamide having the above structural formula by the following IR, NMR and elemental analysis. It was shown that.
IR: 3265cm -1
NH, 1170cm -1 S = O
NMR: 6.75 (1H, NH), 7.20 (1H, aromatic), 7.46-7.60 (3H, aromatic), 7.82 (1H, aromatic), 7.85 (1H,
aromatic)
Elemental analysis value Theoretical value C: 29.38% H: 1.44% N: 2.86%
Analysis value C: 29.54% H: 1.63% N: 2.83%
Ｎ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドを用いる検量線の作成
図１にその概略を示す有機ハロゲン硫黄微量分析装置ＹＳ−１０（ヤナコ機器開発研究所製）を用い前記Ｎ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドによってF,CL,BR,IおよびSについての検量線を同時に作成した。図１に示す装置の燃焼管にＮ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドを入れて９５０oCの高温で燃焼させてガス化し、吸収液（ＮａＨＣＯ３＋Ｈ２Ｏ２＋ヒドラジン）に吸収させ、イオンクロマトグラフ系のカラム（Shodex Si-90: 4E）に展開液と共に導入して分析したところ、図２に示すようにＦ、Ｃｌ、Ｂｒ、ＩおよびSのピークが夫々の位置に存在するイオンクロマトグラムが得られた。
Preparation of calibration curve using N- (2′-iodinated-4′-phenyl bromide) -3-chloride-4-fluorobenzenesulfonamide FIG. 1 shows an organic halogen sulfur microanalyzer YS-10 schematically shown in FIG. F, CL, BR, I and S by the N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorinated benzenesulfonamide using (manufactured by Yanaco Instrument Development Laboratory) A calibration curve was simultaneously created. 1 is charged with N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorobenzenesulfonamide and burned at a high temperature of 950 ° C. And absorbed in an absorbing solution (NaHCO 3 + H 2 O 2 + hydrazine), introduced into an ion chromatography column (Shodex Si-90: 4E) together with a developing solution, and analyzed, as shown in FIG. , Cl, Br, I and S peaks were obtained at each position.
尚、この化合物：Ｎ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドにより作成した夫々の元素についての検量線は図３〜図７に示すように相関係数 t において直線性が極めて高く検量線作成用化合物として用いられることが判明した。すなわち t はＦ、Ｃｌ、Ｂｒ、ＩおよびSについて夫々０．９９７、０．９９９、０．９９８、０．９９９および０．９９９であった。 The calibration curves for the respective elements prepared with this compound: N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorobenzenesulfonamide are shown in FIGS. As shown, it was found that the correlation coefficient t is extremely linear and used as a calibration curve generating compound. That is, t was 0.997, 0.999, 0.998, 0.999 and 0.999 for F, Cl, Br, I and S, respectively.
実際の試料の分析
前記のようにして得られたＮ−（２’−ヨウ化−４’−臭化フェニル）−３−塩化−４−フッ化ベンゼンスルホンアミドによる検量線を用いて各種の実際の試料を分析したところ、表１に示す値（％）が得られ、これら分析値は市販の検量線作成化合物を用いて同一条件で試料を分析した場合の値の差が許容範囲内にあり、こゝで用いた試料は分析の結果ヨウ素を含んでいなかった。
Analysis of actual samples Various actualities were obtained using a calibration curve with N- (2′-iodinated-4′-phenyl bromide) -3-chloro-4-fluorobenzenesulfonamide obtained as described above. When the sample was analyzed, the values (%) shown in Table 1 were obtained, and these analytical values were within the allowable range when the sample was analyzed under the same conditions using commercially available calibration curve preparing compounds. The sample used in this kit did not contain iodine as a result of analysis.
本発明の検量線作成用化合物は、高収率・高純度で得ることができ、自動分析装置のハロゲン・硫黄の一括自動分析法に適用することにより分析時間が著しく短縮され、環境資源材料等の分析の実際において極めて有用である。 The calibration curve preparing compound of the present invention can be obtained in high yield and high purity, and the analysis time can be remarkably shortened by applying it to the automatic analysis method of halogen and sulfur in an automatic analyzer. It is extremely useful in the actual analysis.
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