JP3472800B2 - Alkadiin carboxylate - Google Patents
Alkadiin carboxylateInfo
- Publication number
- JP3472800B2 JP3472800B2 JP2000068580A JP2000068580A JP3472800B2 JP 3472800 B2 JP3472800 B2 JP 3472800B2 JP 2000068580 A JP2000068580 A JP 2000068580A JP 2000068580 A JP2000068580 A JP 2000068580A JP 3472800 B2 JP3472800 B2 JP 3472800B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- integer
- alkadiynecarboxylic
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なアルカジイン
カルボン酸とクラウンエーテルから構成される塩、さら
に詳しくは、固相重合性を有し、金属イオンのセンサー
として有用な１，３−アルカジインカルボン酸塩とその
製造方法に関するものである。TECHNICAL FIELD The present invention relates to a salt composed of a novel alkadiynecarboxylic acid and crown ether, and more specifically, 1,3-alkadiyne having solid-phase polymerizability and useful as a sensor for metal ions. The present invention relates to a carboxylic acid salt and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、金属イオンを簡便に検出する手法
の研究が盛んに行われているが、肉眼による色調の違い
の識別により金属イオンの検出を可能とする化合物はこ
れまで全く見出されていない。2. Description of the Related Art In recent years, researches on methods for simply detecting metal ions have been actively conducted, but compounds capable of detecting metal ions by discriminating a difference in color tone with the naked eye have been found so far. Not not.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、固相重合反
応に基づく色変化の違いによる金属イオンの検出が可能
な新規なアルカジインカルボン酸塩及びその製造方法を
提供することをその課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel alkadiynecarboxylate capable of detecting a metal ion due to a difference in color change based on a solid-state polymerization reaction and a method for producing the same. To do.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。すなわち、本発明によれば、下記一般式
（１）The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, the following general formula (1)
【化５】
（式中、ｐは１〜１２、ｍは１〜４、ｎは１〜４の整数
である）で表わされる１，３−アルカジインカルボン酸
とクラウンエーテルからなる塩が提供される。また、本
発明によれば、下記一般式（２）[Chemical 5] (In the formula, p is 1 to 12, m is 1 to 4, and n is an integer of 1 to 4) A salt of 1,3-alkadiynecarboxylic acid and crown ether is provided. Further, according to the present invention, the following general formula (2)
【化６】
（式中、ｐは１〜１２、ｍは１〜４の整数である）で表
わされる１，３−アルカジインカルボン酸に、一般式
（３）[Chemical 6] (Wherein, p is an integer of 1 to 12 and m is an integer of 1 to 4), the 1,3-alkadiynecarboxylic acid represented by the general formula (3)
【化７】
（式中、ｎは１〜４の整数である）で表されるクラウン
エーテルを反応させる工程から成ることを特徴とするア
ルカジインカルボン酸塩の製造方法が提供される。[Chemical 7] There is provided a method for producing an alkadiynecarboxylic acid salt, which comprises the step of reacting a crown ether represented by the formula (n is an integer of 1 to 4).
【０００５】[0005]
【発明の実施の形態】前記一般式（１）で表わされるア
ルカジインカルボン酸塩は、文献未載の新規な化合物で
ある。式中のｐは１〜１２、好ましくは１０〜１２の整
数である。ｍは、１〜４、好ましくは２〜３の整数であ
る。ｎは、１〜４、好ましくは１〜２の整数である。BEST MODE FOR CARRYING OUT THE INVENTION The alkadiynecarboxylic acid salt represented by the general formula (1) is a novel compound which has not been described in any literature. In the formula, p is an integer of 1 to 12, preferably 10 to 12. m is an integer of 1 to 4, preferably 2 to 3. n is an integer of 1 to 4, preferably 1 to 2.
【０００６】本発明の前記一般式（１）で表わされるア
ルカジインカルボン酸塩は、前記一般式（２）で表わさ
れる１，３−アルカジインカルボン酸化合物を出発原料
として用いて製造することができる。本発明による一般
式（１）のアルカジインカルボン酸塩を製造するには、
前記一般式（２）で表わされる１，３−アルカジインカ
ルボン酸化合物を、前記一般式（３）のアザクラウンと
反応させる。前記一般式（３）におけるｎは、１〜４、
好ましくは３〜４の整数である。前記反応は、塩化メチ
レンのような溶媒中において、好ましくはアルゴンや窒
素等の不活性ガスの界囲気中で、通常、常圧下におい
て、０〜５０℃、好ましくは２５〜４０℃範囲の温度で
攪拌することによって実施される。前記反応によって、
前記一般式（１）で表わされる１，３−アルカジインカ
ルボン酸塩が得られる。反応終了後、溶剤を留去すれ
ば、前記一般式（１）で表わされる本発明の化合物が、
白色結晶として得られる。The alkadiynecarboxylic acid salt represented by the general formula (1) of the present invention can be produced by using the 1,3-alkadiynecarboxylic acid compound represented by the general formula (2) as a starting material. it can. In order to produce the alkadiynecarboxylic acid salt of general formula (1) according to the present invention,
The 1,3-alkadiynecarboxylic acid compound represented by the general formula (2) is reacted with the azacrown of the general formula (3). N in the general formula (3) is 1 to 4,
It is preferably an integer of 3 to 4. The reaction is carried out in a solvent such as methylene chloride, preferably in an atmosphere of an inert gas such as argon or nitrogen, and usually under normal pressure at a temperature of 0 to 50 ° C., preferably 25 to 40 ° C. It is carried out by stirring. By the reaction,
The 1,3-alkadiynecarboxylic acid salt represented by the general formula (1) is obtained. After completion of the reaction, the solvent is distilled off to give the compound of the present invention represented by the general formula (1),
Obtained as white crystals.
【０００７】[0007]
【発明の効果】本発明のアルカジインカルボン酸塩は、
金属イオンを加えることにより、金属イオンの種類によ
る固相重合反応に基づく色変化を示し、金属イオンのセ
ンサー用原料として極めて有用である。The alkadiyne carboxylate of the present invention is
By adding a metal ion, a color change based on a solid-state polymerization reaction depending on the type of the metal ion is exhibited, which is extremely useful as a raw material for a sensor of the metal ion.
【０００８】[0008]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
【０００９】実施例１ 次式で表わされる化合物を反応原料として用いた。Example 1 The compound represented by the following formula was used as a reaction raw material.
【化８】
（式中、ｐ＝１１、ｍ＝３）
この化合物１．４ｇと１−アザ−１８−クラウン−６の
０．８ｇを反応溶媒としての塩化メチレン１００ｍｌ中
で、窒素ガス雰囲気下で、常圧において、２５℃で１２
時間攪拌しながら反応を行った。溶媒を留去して、次式
で表わされる化合物２．２ｇが得られた。[Chemical 8] (In the formula, p = 11, m = 3) 1.4 g of this compound and 0.8 g of 1-aza-18-crown-6 in 100 ml of methylene chloride as a reaction solvent under a nitrogen gas atmosphere at atmospheric pressure. At 12 ° C at 25 ° C
The reaction was carried out with stirring for a time. The solvent was distilled off to obtain 2.2 g of a compound represented by the following formula.
【化９】
（式中のｐ、ｍ、ｎはそれぞれ１１、３、３の整数であ
る）
このアルカジインカルボン酸塩は、白色結晶であり、そ
の融点は約１６０℃であった。[Chemical 9] (In the formula, p, m, and n are integers of 11, 3, and 3, respectively.) This alkadiyne carboxylate salt was white crystals, and its melting point was about 160 ° C.
【００１０】実施例２ 次式で表される化合物を反応原料として用いた。Embodiment 2 The compound represented by the following formula was used as a reaction raw material.
【化１０】
（式中、ｐ＝９、ｍ＝２）
この化合物１．２ｇと１−アザ−１８−クラウン−６の
０．８ｇを反応溶媒としての塩化メチレン１００ｍｌ中
で、窒素ガス雰囲気下で、常圧において、２５℃で１２
時間攪拌しながら反応を行った。溶媒を留去して、次式
で表される化合物２．０ｇが得られた。[Chemical 10] (In the formula, p = 9, m = 2) 1.2 g of this compound and 0.8 g of 1-aza-18-crown-6 in 100 ml of methylene chloride as a reaction solvent under a nitrogen gas atmosphere at atmospheric pressure. At 12 ° C at 25 ° C
The reaction was carried out with stirring for a time. The solvent was distilled off to obtain 2.0 g of a compound represented by the following formula.
【化１１】
（式中のｐ、ｍ、ｎはそれぞれ９、２、３の整数であ
る）
このアルカジインカルボン酸塩は、白色結晶であり、そ
の融点は約１７０℃であった。[Chemical 11] (In the formula, p, m, and n are integers of 9, 2, and 3, respectively.) This alkadiyne carboxylate salt was white crystals, and its melting point was about 170 ° C.
【００１１】実施例３ 次式で表される化合物を反応原料として用いた。Embodiment 3 The compound represented by the following formula was used as a reaction raw material.
【化１２】
（式中、ｐ＝１１、ｍ＝３）
この化合物１．４ｇと１−アザ−１５−クラウン−５の
０．６７ｇを反応溶媒としての塩化メチレン１００ｍｌ
中で、窒素ガス雰囲気下で、常圧において、２５℃で１
２時間攪拌しながら反応を行った。溶媒を留去して、次
式で表される化合物２．０７ｇが得られた。[Chemical 12] (In the formula, p = 11, m = 3) 1.4 g of this compound and 0.67 g of 1-aza-15-crown-5 were added to 100 ml of methylene chloride as a reaction solvent.
In a nitrogen gas atmosphere at atmospheric pressure at 25 ° C for 1
The reaction was carried out with stirring for 2 hours. The solvent was distilled off to obtain 2.07 g of a compound represented by the following formula.
【化１３】
（式中のｌ、ｍ、ｎはそれぞれ１１、３、２の整数であ
る）
このアルカジインカルボン酸塩は、白色結晶であり、そ
の融点は約１４０℃であった。[Chemical 13] (In the formula, l, m, and n are integers of 11, 3, and 2, respectively.) The alkadiyne carboxylate salt was white crystals and had a melting point of about 140 ° C.
【００１２】参考例１
実施例１〜３で得られた本発明のジアセチレン誘導体の
各試料に、リチウム、ナトリウム、カリウムのハロゲン
化物の溶液を加え、乾燥させる。得られた白色固体にコ
バルト６０ガンマー線又は高圧水銀灯による紫外線を照
射したところ、いずれも固相重合し、リチウムは赤色、
ナトリウムは橙色、カリウムは青色に変化し、肉眼で簡
便に識別することができた。Reference Example 1 To each sample of the diacetylene derivative of the present invention obtained in Examples 1 to 3, a solution of a halide of lithium, sodium or potassium is added and dried. When the obtained white solid was irradiated with cobalt 60 gamma rays or ultraviolet rays from a high-pressure mercury lamp, both solid-phase polymerized, lithium was red,
Sodium changed to orange and potassium changed to blue, which could be easily identified by the naked eye.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 57/18 C07C 51/41 C07D 273/01 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C07C 57/18 C07C 51/41 C07D 273/01 CA (STN) REGISTRY (STN)
Claims (2)
である）で表わされる１，３−アルカジインカルボン酸
とクラウンエーテルからなる塩。1. The following general formula (1): (In the formula, p is 1 to 12, m is 1 to 4, and n is an integer of 1 to 4) A salt consisting of 1,3-alkadiynecarboxylic acid and crown ether.
わされる１，３−アルカジインカルボン酸に、一般式
（３） 【化３】 （式中、ｎは１〜４の整数である）で表されるクラウン
エーテルを反応させる工程から成ることを特徴とする、
下記一般式（１） 【化４】 （式中、ｐ、ｍ、ｎは前期と同じ意味を示す）で表わさ
れる塩の製造方法。2. The following general formula (2): (Wherein p is an integer of 1 to 12 and m is an integer of 1 to 4) is added to the 1,3-alkadiynecarboxylic acid represented by the general formula (3): (Wherein n is an integer of 1 to 4), the step of reacting a crown ether represented by the formula,
The following general formula (1): (In the formula, p, m and n have the same meanings as in the preceding period).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068580A JP3472800B2 (en) | 2000-03-13 | 2000-03-13 | Alkadiin carboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068580A JP3472800B2 (en) | 2000-03-13 | 2000-03-13 | Alkadiin carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001253849A JP2001253849A (en) | 2001-09-18 |
| JP3472800B2 true JP3472800B2 (en) | 2003-12-02 |
Family
ID=18587615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000068580A Expired - Lifetime JP3472800B2 (en) | 2000-03-13 | 2000-03-13 | Alkadiin carboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3472800B2 (en) |
-
2000
- 2000-03-13 JP JP2000068580A patent/JP3472800B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001253849A (en) | 2001-09-18 |
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