JPH0753427A - Host compound and clathrate compound - Google Patents
Host compound and clathrate compoundInfo
- Publication number
- JPH0753427A JPH0753427A JP20004393A JP20004393A JPH0753427A JP H0753427 A JPH0753427 A JP H0753427A JP 20004393 A JP20004393 A JP 20004393A JP 20004393 A JP20004393 A JP 20004393A JP H0753427 A JPH0753427 A JP H0753427A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- xylene
- tetrakis
- hydroxyphenyl
- guest
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はホスト化合物及び包接化
合物に係り、更に詳しくはテトラキス（ヒドロキシフェ
ニル）キシレンをホスト化合物とし、ゲスト有機化合物
の捕捉並びに放出を視覚的に認識することができるよう
にした包接化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a host compound and an inclusion compound, and more specifically to tetrakis (hydroxyphenyl) xylene as a host compound so that trapping and release of a guest organic compound can be visually recognized. Clathrate compound.
【０００２】[0002]
【従来の技術】包接化合物は、ホスト分子の作る空洞内
にゲスト分子が入り込んだ構造を有する化合物であり、
近年、選択分離、化学的安定化、不揮発化、粉末化など
の技術分野における応用が期待されている。従来の包接
化合物としては、例えば、特開昭６１−５３２０１号公
報には、１，１，６，６−テトラフェニル−２，４−ヘ
キサジイン−１，６−ジオール又は１，１−ジ（２，４
−ジメチルフェニル）−２−プロピン−１−オールを、
特開昭６２−２２７０１号公報には、１，１’−ビス−
２−ナフトールをそれぞれホストとして、５−クロロ−
２−メチル−４−イソチアゾリン−３−オン（ＣＭＩ）
等をゲストとするもの等が知られている。又、テトラキ
スフェノール類をホストとする包接化合物は、テトラキ
ス（４−ヒドロキシフェニル）エタンをホストとするも
のが知られている（TetrahedronLetters.,33(42),6319
(1992). 参照）。2. Description of the Related Art An inclusion compound is a compound having a structure in which a guest molecule enters a cavity formed by a host molecule,
In recent years, application in the technical fields of selective separation, chemical stabilization, nonvolatization, powderization, etc. is expected. As a conventional clathrate compound, for example, in JP-A-61-53201, 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol or 1,1-di ( 2,4
-Dimethylphenyl) -2-propyn-1-ol,
JP-A-62-22701 discloses 1,1'-bis-
Using 2-naphthol as a host, 5-chloro-
2-Methyl-4-isothiazolin-3-one (CMI)
It is known that guests and the like are guests. In addition, an inclusion compound having tetrakisphenol as a host is known to have tetrakis (4-hydroxyphenyl) ethane as a host (Tetrahedron Letters., 33 (42), 6319).
(1992).).
【０００３】さらに、有機化合物が包接されることによ
り色彩が変化する包接化合物としては特開平３−２３２
８６１号公報に記載されたものが知られている。Further, as an inclusion compound whose color is changed by inclusion of an organic compound, JP-A-3-232 is known.
The one described in Japanese Patent No. 861 is known.
【０００４】[0004]
【発明が解決しようとする問題点】上述の固相系包接化
合物の主流を占めている結合の方法論は水素結合等によ
る分子間（ホスト−ゲスト）相互作用であるが、この作
用を確認する手段としては赤外分光法が唯一の方法であ
り、その応用範囲（例えば、センサー等）に枠をはめる
原因となっていた。The bonding methodology which occupies the mainstream of the above-mentioned solid phase clathrate compounds is intermolecular (host-guest) interaction due to hydrogen bonding, etc., but this effect is confirmed. Infrared spectroscopy is the only method available as a means, and has been a cause of putting a framework within its application range (for example, a sensor).
【０００５】本発明はこのような実情からみてなされた
ものであり、ゲスト有機化合物を包接し得るテトラキス
（ヒドロキシフェニル）キシレンのホスト化合物、及び
このホスト化合物にゲスト有機化合物を包接させてな
る、有効成分の安定性、取り扱い性、加工性等を改善
し、しかも、ゲスト有機化合物の捕捉並びに放出を視覚
的に認識可能な包接化合物を提供することを目的とす
る。The present invention has been made in view of such circumstances, and comprises a host compound of tetrakis (hydroxyphenyl) xylene capable of including a guest organic compound, and a guest organic compound included in the host compound. It is an object of the present invention to provide a clathrate compound which improves the stability, handleability, processability, etc. of an active ingredient and is capable of visually recognizing trapping and release of a guest organic compound.
【０００６】[0006]
【問題点を解決するための手段】本発明は上記の問題点
を解決すべく鋭意研究をした結果、特定のテトラキス
（ヒドロキシフェニル）キシレン類のホスト化合物が、
ゲストとする有機化合物の捕捉即ち、包接化合物の生
成、及びゲストの放出に伴い、自らの色彩を変化させる
ことを見いだし、本発明を完成した。以下本発明を詳細
に説明する。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present invention revealed that a specific tetrakis (hydroxyphenyl) xylene host compound was
The present invention has been completed by discovering that the color of the organic compound used as a guest is changed, that is, the inclusion compound is generated, and the guest is released. The present invention will be described in detail below.
【０００７】本発明は、一般式化２で示されるテトラキ
ス（ヒドロキシフェニル）キシレンからなるホスト化合
物、及び該化合物をホスト化合物とする包接化合物であ
る。The present invention is a host compound composed of tetrakis (hydroxyphenyl) xylene represented by the general formula 2, and an inclusion compound using the compound as a host compound.
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】上記一般式化２において、Ｒ1 〜Ｒ16は、
それぞれ水素原子、Ｆ、Ｃｌ、Ｂｒ、Ｉ等のハロゲン原
子、メチル基、エチル基、イソプロピル基、プロピル
基、ブチル基、ｔ−ブチル基、ｓｅｃ−ブチル基等のア
ルキル基、メトキシ基、エトキシ基、イソプロポキシ
基、ブトキシ基、ｔ−ブトキシ基等のアルコキシ基から
なる群より選ばれるいずれか一種を表す。In the above general formula 2, R 1 to R 16 are
Hydrogen atom, halogen atom such as F, Cl, Br, I, etc., alkyl group such as methyl group, ethyl group, isopropyl group, propyl group, butyl group, t-butyl group, sec-butyl group, methoxy group, ethoxy group, etc. , Any one selected from the group consisting of alkoxy groups such as isopropoxy group, butoxy group and t-butoxy group.
【００１０】上記一般式化２に示される化合物のほか、
本発明においては、水酸基がベンゼン環の２位や３位に
置換したテトラキス（ヒドロキシフェニル）キシレンも
包接能を有するものであればホスト化合物として使用す
ることができる。In addition to the compound represented by the above general formula 2,
In the present invention, tetrakis (hydroxyphenyl) xylene having a hydroxyl group substituted at the 2- or 3-position of the benzene ring can also be used as a host compound as long as it has an inclusion ability.
【００１１】本発明のテトラキス（ヒドロキシフェニ
ル）キシレン類としては、例えば、α，α，α’，α’
−テトラキス（４−ヒドロキシフェニル）−ｐ−キシレ
ン、α，α，α’，α’−テトラキス（４−ヒドロキシ
フェニル）−ｍ−キシレン、α，α，α’，α’−テト
ラキス（４−ヒドロキシフェニル）−ｏ−キシレン、
α，α，α’，α’−テトラキス（４−ヒドロキシ−３
−メチルフェニル）−ｐ−キシレン、α，α，α’，
α’−テトラキス（４−ヒドロキシ−３−クロロフェニ
ル）−ｐ−キシレン、α，α，α’，α’−テトラキス
（４−ヒドロキシ−３−フロロフェニル）−ｐ−キシレ
ン、α，α，α’，α’−テトラキス（４−ヒドロキシ
−３−エチルフェニル）−ｐ−キシレン、α，α，
α’，α’−テトラキス（４−ヒドロキシ−３−イソプ
ロピルフェニル）−ｐ−キシレン、α，α，α’，α’
−テトラキス（４−ヒドロキシ−３−クロロフェニル）
−ｍ−キシレン、α，α，α’，α’−テトラキス（４
−ヒドロキシ−３−フロロフェニル）−ｍ−キシレン、
α，α，α’，α’−テトラキス（４−ヒドロキシ−３
−メチルフェニル）−ｍ−キシレン、α，α，α’，
α’−テトラキス（４−ヒドロキシ−３−エチルフェニ
ル）−ｍ−キシレン、α，α，α’，α’−テトラキス
（４−ヒドロキシ−３−イソプロピルフェニル）−ｍ−
キシレン、α，α，α’，α’−テトラキス（４−ヒド
ロキシ−３−メチルフェニル）−ｏ−キシレン、α，
α，α’，α’−テトラキス（４−ヒドロキシ−３−ク
ロロフェニル）−ｏ−キシレン、α，α，α’，α’−
テトラキス（４−ヒドロキシ−３−フロロフェニル）−
ｏ−キシレン、α，α，α’，α’−テトラキス（４−
ヒドロキシ−３−エチルフェニル）−ｏ−キシレン、
α，α，α’，α’−テトラキス（４−ヒドロキシ−３
−イソプロピルフェニル）−ｏ−キシレン、α，α，
α’，α’−テトラキス（４−ヒドロキシ−３−ｔ−ブ
チルフェニル）−ｐ−キシレン、α，α，α’，α’−
テトラキス（４−ヒドロキシ−３−ブロモフェニル）−
ｐ−キシレン、α，α，α’，α’−テトラキス（４−
ヒドロキシ−３−ヨードフェニル）−ｐ−キシレン、
α，α，α’，α’−テトラキス（４−ヒドロキシ−３
−メトキシフェニル）−ｐ−キシレン、α，α，α’，
α’−テトラキス（４−ヒドロキシ−３−エトキシフェ
ニル）−ｐ−キシレン、α，α，α’，α’−テトラキ
ス（４−ヒドロキシ−３−イソプロポキシフェニル）−
ｐ−キシレン、α，α，α’，α’−テトラキス（４−
ヒドロキシ−３−ｔ−ブトキシフェニル）−ｐ−キシレ
ン、α，α，α’，α’−テトラキス（３−ヒドロキシ
フェニル）−ｐ−キシレン、α，α，α’，α’−テト
ラキス（３−ヒドロキシ−４−クロロフェニル）−ｐ−
キシレン、α，α，α’，α’−テトラキス（３−ヒド
ロキシ−４−ブロモフェニル）−ｐ−キシレン、α，
α，α’，α’−テトラキス（３−ヒドロキシ−４−ヨ
ードフェニル）−ｐ−キシレン、α，α，α’，α’−
テトラキス（３−ヒドロキシ−４−メトキシフェニル）
−ｐ−キシレン、α，α，α’，α’−テトラキス（３
−ヒドロキシ−４−エトキシフェニル）−ｐ−キシレ
ン、α，α，α’，α’−テトラキス（２−ヒドロキシ
フェニル）−ｐ−キシレン、α，α，α’，α’−テト
ラキス（２−ヒドロキシ−４−クロロフェニル）−ｐ−
キシレン、α，α，α’，α’−テトラキス（２−ヒド
ロキシ−４−メチルフェニル）−ｐ−キシレン、α，
α，α’，α’−テトラキス（２−ヒドロキシ−４−メ
トキシフェニル）−ｐ−キシレン、、α，α，α’，
α’−テトラキス（４−ヒドロキシ−３，５−ジクロロ
フェニル）−ｐ−キシレン、α，α，α’，α’−テト
ラキス（４−ヒドロキシ−３，５−ジメチルフェニル）
−ｐ−キシレン、α，α，α’，α’−テトラキス（４
−ヒドロキシ−３−クロロ−５−メチルフェニル）−ｐ
−キシレン、α，α，α’，α’−テトラキス（４−ヒ
ドロキシフェニル）−３−クロロ−ｐ−キシレン、α，
α，α’，α’−テトラキス（４−ヒドロキシフェニ
ル）−３−フロロ−ｐ−キシレン、α，α，α’，α’
−テトラキス（４−ヒドロキシフェニル）−３−メチル
−ｐ−キシレン、α，α，α’，α’−テトラキス（４
−ヒドロキシフェニル）−３−メトキシ−ｐ−キシレ
ン、α，α−ビス（４−ヒドロキシフェニル）−α’，
α’−ビス（３−クロロ−４−ヒドロキシフェニル）−
ｐ−キシレン、α，α−ビス（４−ヒドロキシフェニ
ル）−α’，α’−ビス（３−フロロ−４−ヒドロキシ
フェニル）−ｐ−キシレン、α，α−ビス（４−ヒドロ
キシフェニル）−α’，α’−ビス（３−メチル−４−
ヒドロキシフェニル）−ｐ−キシレン、α，α−ビス
（４−ヒドロキシフェニル）−α’，α’−ビス（３−
メトキシ−４−ヒドロキシフェニル）−ｐ−キシレン、
α，α−ビス（４−ヒドロキシフェニル）−α’，α’
−ビス（３−フロロ−４−ヒドロキシフェニル）−ｐ−
キシレン、α，α，α’−トリス（４−ヒドロキシフェ
ニル）−α’−３−クロロフェニル−ｐ−キシレン、
α，α，α’−トリス（４−ヒドロキシフェニル）−
α’−３−メチルフェニル−ｐ−キシレン、α，α，
α’−トリス（４−ヒドロキシフェニル）−α’−３−
メトキシフェニル−ｐ−キシレン、α，α，α’−トリ
ス（４−ヒドロキシフェニル）−α’−３−フロロフェ
ニル−ｐ−キシレン等を挙げることができる。The tetrakis (hydroxyphenyl) xylenes of the present invention include, for example, α, α, α ', α'.
-Tetrakis (4-hydroxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxyphenyl) -m-xylene, α, α, α', α'-tetrakis (4-hydroxy) Phenyl) -o-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methylphenyl) -p-xylene, α, α, α ′,
α'-tetrakis (4-hydroxy-3-chlorophenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3-fluorophenyl) -p-xylene, α, α, α' , Α′-Tetrakis (4-hydroxy-3-ethylphenyl) -p-xylene, α, α,
α ', α'-tetrakis (4-hydroxy-3-isopropylphenyl) -p-xylene, α, α, α', α '
-Tetrakis (4-hydroxy-3-chlorophenyl)
-M-xylene, α, α, α ', α'-tetrakis (4
-Hydroxy-3-fluorophenyl) -m-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methylphenyl) -m-xylene, α, α, α ′,
α′-tetrakis (4-hydroxy-3-ethylphenyl) -m-xylene, α, α, α ′, α′-tetrakis (4-hydroxy-3-isopropylphenyl) -m-
Xylene, α, α, α ′, α′-tetrakis (4-hydroxy-3-methylphenyl) -o-xylene, α,
α, α ', α'-tetrakis (4-hydroxy-3-chlorophenyl) -o-xylene, α, α, α', α'-
Tetrakis (4-hydroxy-3-fluorophenyl)-
o-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-ethylphenyl) -o-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Isopropylphenyl) -o-xylene, α, α,
α ', α'-tetrakis (4-hydroxy-3-t-butylphenyl) -p-xylene, α, α, α', α'-
Tetrakis (4-hydroxy-3-bromophenyl)-
p-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-iodophenyl) -p-xylene,
α, α, α ', α'-tetrakis (4-hydroxy-3
-Methoxyphenyl) -p-xylene, α, α, α ′,
α'-Tetrakis (4-hydroxy-3-ethoxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3-isopropoxyphenyl)-
p-xylene, α, α, α ′, α′-tetrakis (4-
Hydroxy-3-t-butoxyphenyl) -p-xylene, α, α, α ′, α′-tetrakis (3-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetrakis (3- Hydroxy-4-chlorophenyl) -p-
Xylene, α, α, α ′, α′-tetrakis (3-hydroxy-4-bromophenyl) -p-xylene, α,
α, α ', α'-tetrakis (3-hydroxy-4-iodophenyl) -p-xylene, α, α, α', α'-
Tetrakis (3-hydroxy-4-methoxyphenyl)
-P-xylene, α, α, α ', α'-tetrakis (3
-Hydroxy-4-ethoxyphenyl) -p-xylene, α, α, α ', α'-tetrakis (2-hydroxyphenyl) -p-xylene, α, α, α', α'-tetrakis (2-hydroxy) -4-chlorophenyl) -p-
Xylene, α, α, α ′, α′-tetrakis (2-hydroxy-4-methylphenyl) -p-xylene, α,
α, α ′, α′-tetrakis (2-hydroxy-4-methoxyphenyl) -p-xylene, α, α, α ′,
α'-tetrakis (4-hydroxy-3,5-dichlorophenyl) -p-xylene, α, α, α ', α'-tetrakis (4-hydroxy-3,5-dimethylphenyl)
-P-xylene, α, α, α ', α'-tetrakis (4
-Hydroxy-3-chloro-5-methylphenyl) -p
-Xylene, α, α, α ', α'-tetrakis (4-hydroxyphenyl) -3-chloro-p-xylene, α,
α, α ′, α′-tetrakis (4-hydroxyphenyl) -3-fluoro-p-xylene, α, α, α ′, α ′
-Tetrakis (4-hydroxyphenyl) -3-methyl-p-xylene, α, α, α ', α'-tetrakis (4
-Hydroxyphenyl) -3-methoxy-p-xylene, α, α-bis (4-hydroxyphenyl) -α ′,
α'-bis (3-chloro-4-hydroxyphenyl)-
p-xylene, α, α-bis (4-hydroxyphenyl) -α ′, α′-bis (3-fluoro-4-hydroxyphenyl) -p-xylene, α, α-bis (4-hydroxyphenyl)- α ', α'-bis (3-methyl-4-
Hydroxyphenyl) -p-xylene, α, α-bis (4-hydroxyphenyl) -α ′, α′-bis (3-
Methoxy-4-hydroxyphenyl) -p-xylene,
α, α-bis (4-hydroxyphenyl) -α ', α'
-Bis (3-fluoro-4-hydroxyphenyl) -p-
Xylene, α, α, α′-tris (4-hydroxyphenyl) -α′-3-chlorophenyl-p-xylene,
α, α, α'-tris (4-hydroxyphenyl)-
α′-3-methylphenyl-p-xylene, α, α,
α'-tris (4-hydroxyphenyl) -α'-3-
Examples thereof include methoxyphenyl-p-xylene, α, α, α′-tris (4-hydroxyphenyl) -α′-3-fluorophenyl-p-xylene.
【００１２】本発明のテトラキス（ヒドロキシフェニ
ル）キシレンに包接されるゲスト有機化合物としては、
水、メタノール、エタノール、イソプロパノール、２−
プロパノール等のアルコール類、アセトニトリル、アセ
トン、メチルエチルケトン等のケトン類、テトラヒドロ
フラン、１，４−ジオキサン、エチルエーテル等のエー
テル類、酢酸メチル、酢酸エチル、酢酸イソプロピル等
の酢酸エステル類、置換されていてもよいピリジン、置
換されていてもよいピロール、置換されていてもよいピ
リミジン、置換されていてもよいピリダジン、置換され
ていてもよいイミダゾール、置換されていてもよいピラ
ゾール等の含窒素ヘテロ環化合物、酢酸、プロピオン
酸、クエン酸、スルファミン酸等の有機酸、５−クロロ
−２−メチル−４−イソチアゾリン−３−オン（ＣＭ
Ｉ）、ヒノキチオール、シネオール、チモール、メント
ール、テルピネオール、ボルネオール、ノポール、シト
ラール、シトロネオール、シトラネオール、リナロー
ル、ジメチルオクタノール、キンモクセイ、ジャスミ
ン、レモン等の精油、香料類等どを例示することができ
る。The guest organic compound included in the tetrakis (hydroxyphenyl) xylene of the present invention includes:
Water, methanol, ethanol, isopropanol, 2-
Alcohols such as propanol, ketones such as acetonitrile, acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, 1,4-dioxane and ethyl ether, acetic acid esters such as methyl acetate, ethyl acetate and isopropyl acetate, even if substituted Good pyridine, optionally substituted pyrrole, optionally substituted pyrimidine, optionally substituted pyridazine, optionally substituted imidazole, optionally substituted nitrogen-containing heterocyclic compound such as pyrazole, Organic acids such as acetic acid, propionic acid, citric acid, sulfamic acid, 5-chloro-2-methyl-4-isothiazolin-3-one (CM
I), hinokitiol, cineole, thymol, menthol, terpineol, borneol, nopol, citral, citroneol, citraneol, linalool, dimethyloctanol, quince wax, jasmine, essential oils such as lemon, fragrances and the like.
【００１３】本発明の包接化合物は、通常、ゲストとな
る有機化合物とホストとなる本発明のテトラキス（ヒド
ロキシフェニル）キシレン類とを、場合によっては不活
性溶媒存在下に常温〜１００℃で数分間〜数時間攪拌し
て反応させることにより得ることができる。The clathrate compound of the present invention usually comprises an organic compound as a guest and a tetrakis (hydroxyphenyl) xylene of the present invention as a host at room temperature to 100 ° C. in the presence of an inert solvent. It can be obtained by stirring for 1 minute to several hours to react.
【００１４】以下、本発明を実施例に沿って更に詳細に
説明する。 （実施例１） （ホスト化合物）ＴＸＰ（α，α，α’，α’−テトラ
キス（4-ヒドロキシフェニル）−ｐ−キシレン）の合成 撹拌棒，温度計を備えた５００ｍｌ− 3口フラスコに、
テレフタルアルデヒド１０．０g （０．０７１ｍｏ
ｌ）、とフェノール７０．０ｇ（０．７４ｍｏｌ）を仕
込み、５０℃で撹拌しながら３５％塩酸５ｍｌを滴下し
た。ついで５０℃でそのまま３時間撹拌し反応を終了さ
せた。反応終了後、未反応のフェノールを１００℃で減
圧除去し、橙色の固化物を得た。この固化物をクロロホ
ルムで洗浄し、１００℃で真空乾燥させて、淡橙色の粉
末３２．０ｇ（収率９１．２％）を得た。この粉末が
α，α，α’，α’−テトラキス（４−ヒドロキシフェ
ニル）−ｐ−キシレンであることを赤外吸収スペクトル
及び核磁気共鳴スペクトルで確認した。ＴＸＰのＨ1 −
ＮＭＲスペクトル（溶媒：ｄ4-ＭｅＯＨ，内部標準：Ｔ
ＭＳ）を図１に、ＩＲスペクトル（ＫＢｒ法、以下同
じ）を図２にそれぞれ示す。The present invention will be described in more detail below with reference to examples. Example 1 (Host Compound) Synthesis of TXP (α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene) In a 500 ml-3 neck flask equipped with a stir bar and thermometer,
Terephthalaldehyde 10.0g (0.071mo
1) and 70.0 g (0.74 mol) of phenol were charged, and 5 ml of 35% hydrochloric acid was added dropwise while stirring at 50 ° C. Then, the reaction was terminated by stirring at 50 ° C. for 3 hours as it was. After the reaction was completed, unreacted phenol was removed under reduced pressure at 100 ° C. to obtain an orange solidified product. The solidified product was washed with chloroform and vacuum dried at 100 ° C. to obtain 32.0 g (yield 91.2%) of pale orange powder. It was confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum that this powder was α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene. H 1 of TXP
NMR spectrum (solvent: d 4 -MeOH, internal standard: T
MS) is shown in FIG. 1, and IR spectrum (KBr method, the same applies hereinafter) is shown in FIG.
【００１５】（実施例２）試料：１〜５の製造 ホスト化合物としてＴＸＰ〔α，α，α’，α’−テト
ラキス（４−ヒドロキシフェニル）−ｐ−キシレン〕
２．１１ｍｍｏｌ（１．０ｇ）を、ゲストとしたい有機
化合物１０ｍｌ中に加えて、ＴＸＰが完全に溶解した後
さらに所定の時間反応させ、この反応液を室温で放置し
て結晶を析出させた。この析出物を濾別後、室温にて真
空乾燥を行い、本発明包接化合物である試料、１〜５を
得た。包接化合物の確認は、ＴＧ−ＤＴＡ測定，ＩＲ測
定により行った。また、包接化合物の色調は測色色差計
を用いて測定した。Ｃ．Ｉ．Ｅ．（Ｃｏｍｍｉｓｉｏｎ
Ｉｎｔｅｒｎａｔｉｏｎａｌ ｄ’Ｅｃｌａｒｉａｇ
ｅ）表示法に基づいた色測定値を表１に纏めて示す。(Example 2) Preparation of samples: 1 to 5 TXP [α, α, α ', α'-tetrakis (4-hydroxyphenyl) -p-xylene] as a host compound
2.11 mmol (1.0 g) was added to 10 ml of an organic compound to be used as a guest, and TXP was completely dissolved and then reacted for a predetermined time, and the reaction solution was allowed to stand at room temperature to precipitate crystals. After this precipitate was separated by filtration, it was vacuum dried at room temperature to obtain Samples 1 to 5 as the inclusion compound of the present invention. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E. (Commission
International d'Eclariag
e) Color measurement values based on the display method are summarized in Table 1.
【００１６】得られた本発明の包接化合物でゲスト化合
物がアセトニトリルであるもの（試料２）のＩＲスペク
トルを図３、１，４−ジオキサンであるもの（試料３）
のＩＲスペクトルを図４、ベンズアルデヒドのもの（試
料４）のＩＲスペクトルを図５、ピリジンのもの（試料
５）のＩＲスペクトルを図６にそれぞれ示す。The IR spectrum of the obtained inclusion compound of the present invention in which the guest compound is acetonitrile (Sample 2) is shown in FIG. 3, which is 1,4-dioxane (Sample 3).
The IR spectrum of benzaldehyde (Sample 4) is shown in FIG. 5, and the IR spectrum of pyridine (Sample 5) is shown in FIG.
【００１７】（実施例３）試料：６の製造 ホスト化合物としてＴＸＰ２．１１ｍｍｏｌ（１．０
ｇ）を、ゲスト化合物のベンゼン１０ｍｌ中に加え、ベ
ンゼンが煮沸するまで加熱撹拌した後、反応液を室温ま
で放置して結晶を析出させた。結晶を濾別後、室温にて
真空乾燥を行い、本発明包接化合物である試料、６を得
た。包接化合物の確認は、ＴＧ−ＤＴＡ測定、ＩＲ測定
により行った。また、包接化合物の色調は測色色差計を
用いて測定した。Ｃ．Ｉ．Ｅ．（Ｃｏｍｍｉｓｉｏｎ
Ｉｎｔｅｒｎａｔｉｏｎａｌ ｄ’Ｅｃｌａｒｉａｇ
ｅ）表示法に基づいた色測定値を表１に示す。(Example 3) Preparation of sample: 6 2.11 mmol (1.0) of TXP as a host compound
g) was added to 10 ml of benzene as a guest compound, and the mixture was heated and stirred until benzene boiled, and then the reaction solution was allowed to stand at room temperature to precipitate crystals. After the crystals were separated by filtration, vacuum drying was carried out at room temperature to obtain a clathrate compound sample 6 of the present invention. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E. (Commission
International d'Eclariag
e) Table 1 shows color measurement values based on the display method.
【００１８】（実施例４）試料：７の製造 メタノール 5ｍｌ中にＴＸＰ２．１１ｍｍｏｌ（１．０
ｇ）を加え、ＴＸＰが完全に溶解するまで加温しながら
撹拌した。これにゲスト化合物のシネオール５ｍｌを徐
々に滴下し、５０℃で５分撹拌しながら反応させた後、
この反応液を室温で放置して結晶を析出させた。この析
出物を濾別後、室温にて真空乾燥を行い、本発明包接化
合物である試料、７を得た。包接化合物の確認は、ＴＧ
−ＤＴＡ測定，ＩＲ測定により行った。また、包接化合
物の色調は測色色差計を用いて測定した。Ｃ．Ｉ．Ｅ．
（Ｃｏｍｍｉｓｉｏｎ Ｉｎｔｅｒｎａｔｉｏｎａｌ
ｄ’Ｅｃｌａｒｉａｇｅ）表示法に基づいた色測定値を
表１に示す。また、試料７のＩＲスペクトルを図７に示
す。(Example 4) Preparation of sample: 7 TXP 2.11 mmol (1.0
g) was added and stirred with warming until the TXP was completely dissolved. 5 ml of the guest compound, cineole, was gradually added dropwise to this, and the mixture was reacted at 50 ° C. for 5 minutes with stirring.
The reaction solution was left at room temperature to precipitate crystals. After this precipitate was separated by filtration, it was vacuum dried at room temperature to obtain Sample 7, which was the inclusion compound of the present invention. The inclusion compound can be confirmed by TG
-DTA measurement and IR measurement were performed. Further, the color tone of the clathrate compound was measured using a colorimetric color difference meter. C. I. E.
(Commission International
Table 1 shows the color measurement values based on the d'Eclarage) notation. The IR spectrum of Sample 7 is shown in FIG.
【００１９】（実施例５）試料：８の製造 水１０ｍｌ中にＴＸＰ２．１１ｍｍｏｌ（１．０ｇ）を
加え、５０℃で２０分撹拌する。ここへケーソンＷＴ
（ローム＆ハース社製）２０ｇ（ＣＭＩとして１１．４
ｍｍｏｌ）を徐々に滴下し、２５℃で２４時間撹拌しな
がら反応させた。ついで、この液を室温でしばらく静置
した後、沈澱物を吸引濾過し、濾過物を室温にて真空乾
燥して赤橙色粉末の試料８を得た。包接化合物の確認
は、ＴＧ−ＤＴＡ測定，ＩＲ測定により行った。また、
包接化合物の色調は測色色差計を用いて測定した。Ｃ．
Ｉ．Ｅ．（Ｃｏｍｍｉｓｉｏｎ Ｉｎｔｅｒｎａｔｉｏ
ｎａｌ ｄ’Ｅｃｌａｒｉａｇｅ）表示法に基づいた色
測定値を表２に示す。なお、実施例５で使用した水溶性
殺菌剤（ケーソンWT）の分析値は、下記のとおりであ
る。 ＣＭＩ（5-クロロ-2- メチル-4- イソチアゾリン-3- オン）： 10.1 wt% ＭＩ（2-メチル-4- イソチアゾリン-3- オン） ： 3.8 wt% 残部： 塩化マグネシウム＋硝酸マグネシウム＋水 また、試料８のＩＲスペクトルを図８に示す。(Example 5) Preparation of sample: 8 2.11 mmol (1.0 g) of TXP was added to 10 ml of water, and the mixture was stirred at 50 ° C for 20 minutes. Here caisson WT
(Rohm & Haas) 20g (11.4 as CMI
(mmol) was gradually added dropwise, and the mixture was reacted at 25 ° C. for 24 hours while stirring. Then, this liquid was allowed to stand at room temperature for a while, the precipitate was suction-filtered, and the filtered product was vacuum dried at room temperature to obtain a red-orange powder sample 8. The inclusion compound was confirmed by TG-DTA measurement and IR measurement. Also,
The color tone of the clathrate compound was measured using a colorimeter. C.
I. E. (Commission Internet
Table 2 shows the color measurement values based on the nal d'Eclairage) display method. The analytical values of the water-soluble bactericide (Caisson WT) used in Example 5 are as follows. CMI (5-chloro-2-methyl-4-isothiazolin-3-one): 10.1 wt% MI (2-methyl-4-isothiazolin-3-one): 3.8 wt% Remainder: magnesium chloride + magnesium nitrate + water The IR spectrum of Sample 8 is shown in FIG.
【００２０】（実施例６）試料：１〜５のゲスト化合物
再放出に伴う色調変化 実施例１で得られた包接化合物を各々ドライヤーの熱風
にさらしてゲスト化合物の放出試験を行ったところ、各
包接化合物は変色して各々元のホスト化合物の色に戻っ
た。(Example 6) Sample: Change in color tone due to re-release of guest compounds 1 to 5 The inclusion compounds obtained in Example 1 were each exposed to the hot air of a dryer to perform a guest compound release test. The color of each clathrate compound changed to the original color of the host compound.
【００２１】この結果より、本発明のホスト化合物と、
このホスト化合物にゲスト化合物を包接してなる本発明
の包接化合物とは色が異なり、変色によりゲスト化合物
の有無を知ることができることが明かである。From these results, the host compound of the present invention,
It is clear that the host compound has a different color from the clathrate compound of the present invention in which the guest compound is clathrated, and the presence or absence of the guest compound can be known by the color change.
【００２２】（実施例７）試料：７のゲスト化合物の徐
放性 実施例３で得られた試料７及び比較試料１，８−シネオ
ール単独のそれぞれを、ゲスト化合物換算で０．６ｇと
なるようにシャーレに採り、２５℃に保持したデシケー
ター中にセットした。これに乾燥空気を２５０ｍｌ／分
で導入し、経時的に重量減少を測定した。その結果を表
３に示す。表３より、本発明の包接化合物は有効成分の
徐放性に優れることが明かである。(Example 7) Sample: Sustained release of guest compound of 7 Sample 7 obtained in Example 3 and comparative sample 1,8-cineole alone were adjusted to 0.6 g in terms of guest compound. Then, it was collected in a petri dish and set in a desiccator kept at 25 ° C. Dry air was introduced into this at a rate of 250 ml / min, and the weight loss was measured over time. The results are shown in Table 3. From Table 3, it is clear that the clathrate compound of the present invention is excellent in sustained release of the active ingredient.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】本発明は、ゲストとなる有機化合物を包
接することによりホスト化合物の色調が変化する包接化
合物である。従来、ゲスト分子が包接されているか否か
は視覚のみでは判断できなかったが、本発明の包接化合
物によれば工業用殺菌剤、各種香料、精油などのゲスト
有機化合物の捕捉並びに放出を視覚的に認識可能な包接
化合物が提供される。INDUSTRIAL APPLICABILITY The present invention is an inclusion compound in which the color tone of a host compound is changed by including an organic compound as a guest. Conventionally, it was not possible to determine whether or not the guest molecule was clathrated only by the visual sense, but according to the clathrate compound of the present invention, industrial fungicides, various flavors, trapping and release of guest organic compounds such as essential oils can be performed. A visually recognizable inclusion compound is provided.
【００２７】さらに、本発明のホスト化合物であるテト
ラキス（ヒドロキシフェニル）キシレン類は、広範囲な
有機化合物を包接することができ、ホスト化合物の安定
性、取扱性、加工性などが改善される。Furthermore, the host compound of the present invention, tetrakis (hydroxyphenyl) xylene, can include a wide range of organic compounds, and the stability, handleability, processability and the like of the host compound are improved.
【図１】本発明のゲスト化合物であるＴＸＰのＨ1 −Ｎ
ＭＲスペクトルFIG. 1 H 1 —N of TXP, a guest compound of the present invention
MR spectrum
【図２】本発明のゲスト化合物であるＴＸＰのＩＲスペ
クトルFIG. 2 is an IR spectrum of TXP which is a guest compound of the present invention.
【図３】本発明の包接化合物である試料２のＩＲスペク
トルFIG. 3 is an IR spectrum of Sample 2 which is an inclusion compound of the present invention.
【図４】本発明の包接化合物である試料３のＩＲスペク
トルFIG. 4 is an IR spectrum of Sample 3, which is an inclusion compound of the present invention.
【図５】本発明の包接化合物である試料４のＩＲスペク
トルFIG. 5: IR spectrum of sample 4 which is an inclusion compound of the present invention
【図６】本発明の包接化合物である試料５のＩＲスペク
トルFIG. 6 is an IR spectrum of Sample 5, which is an inclusion compound of the present invention.
【図７】本発明の包接化合物である試料７のＩＲスペク
トルFIG. 7: IR spectrum of sample 7, which is an inclusion compound of the present invention
【図８】本発明の包接化合物である試料８のＩＲスペク
トルFIG. 8 is an IR spectrum of Sample 8 which is an inclusion compound of the present invention.
Claims (2)
キシフェニル）キシレンからなるホスト化合物。 【化１】 （式中、Ｒ1 〜Ｒ16は、それぞれ水素原子、ハロゲン原
子、アルキル基及びアルコキシ基からなる群から選ばれ
る一種を表す。）1. A host compound comprising tetrakis (hydroxyphenyl) xylene represented by the general formula 1. [Chemical 1] (In the formula, each of R 1 to R 16 represents one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group.)
フェニル）キシレンと、ゲスト有機化合物とからなるこ
とを特徴とする包接化合物。2. An inclusion compound comprising the tetrakis (hydroxyphenyl) xylene according to claim 1 and a guest organic compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20004393A JP3670026B2 (en) | 1993-06-10 | 1993-07-19 | Host compound and inclusion compound |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16515693 | 1993-06-10 | ||
| JP5-165156 | 1993-06-10 | ||
| JP20004393A JP3670026B2 (en) | 1993-06-10 | 1993-07-19 | Host compound and inclusion compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0753427A true JPH0753427A (en) | 1995-02-28 |
| JP3670026B2 JP3670026B2 (en) | 2005-07-13 |
Family
ID=26489994
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|---|---|---|---|
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6831379B2 (en) | 2000-04-19 | 2004-12-14 | Kabushiki Kaisha Yaskawa Denki | Permanent magnet synchronous linear motor |
| JP2009196918A (en) * | 2008-02-20 | 2009-09-03 | Jsr Corp | Arene compound |
| DE112008002447T5 (en) | 2007-09-14 | 2010-07-22 | Thk Co., Ltd. | Linear motor and method for reducing screen phenomena |
| DE112011102025T5 (en) | 2010-06-16 | 2013-03-21 | Thk Co., Ltd. | linear motor |
-
1993
- 1993-07-19 JP JP20004393A patent/JP3670026B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6831379B2 (en) | 2000-04-19 | 2004-12-14 | Kabushiki Kaisha Yaskawa Denki | Permanent magnet synchronous linear motor |
| DE112008002447T5 (en) | 2007-09-14 | 2010-07-22 | Thk Co., Ltd. | Linear motor and method for reducing screen phenomena |
| US8030804B2 (en) * | 2007-09-14 | 2011-10-04 | Thk Co., Ltd. | Linear motor and linear motor cogging reduction method |
| JP2009196918A (en) * | 2008-02-20 | 2009-09-03 | Jsr Corp | Arene compound |
| DE112011102025T5 (en) | 2010-06-16 | 2013-03-21 | Thk Co., Ltd. | linear motor |
Also Published As
| Publication number | Publication date |
|---|---|
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