JPH08183744A - Production of inclusion compound - Google Patents
Production of inclusion compoundInfo
- Publication number
- JPH08183744A JPH08183744A JP6340280A JP34028094A JPH08183744A JP H08183744 A JPH08183744 A JP H08183744A JP 6340280 A JP6340280 A JP 6340280A JP 34028094 A JP34028094 A JP 34028094A JP H08183744 A JPH08183744 A JP H08183744A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- guest
- inclusion
- host
- dissolved
- 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
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は効率的に包接化合物を製
造する方法に関する。TECHNICAL FIELD The present invention relates to a method for efficiently producing an inclusion compound.
【０００２】[0002]
【従来の技術】ホスト化合物を用いた包接化合物、特に
包接錯体の製法としては、多分子系ホストでは従来、 ア）ホスト化合物を溶解した溶液中に、ゲスト化合物を
溶解した溶液を添加する方法（特開昭６１−５３２０
１、特公平３−３３１２１、特開平５−４９７８）、 イ）ゲスト及びホスト化合物の溶液とする方法（特開昭
６０−２２２８４７、特開昭６２−１４２１４７、特開
平５−１６３１８７、特開平６−７２９０３）、 ウ）ホスト化合物が不溶か難溶性の有機溶剤にゲスト化
合物を溶解し、水の非存在下でホスト化合物を添加する
方法（特開平３−１７８９０６）、 エ）ホスト化合物の懸濁水中にゲスト化合物の水溶液を
添加、反応させる方法（特開平４−３１６５６４）、 オ）粉末ゲスト化合物と粉末ホスト化合物とを混合する
方法（特開昭６３−３５５３３）、 カ）固体ホスト化合物と液状または加熱融解した液状ゲ
スト化合物とを混合する方法（特開昭６０−２６０３８
７、特開昭６２−１６０２７９、特開平１−１６０９２
５、特開平４−１５０９１７、特開平５−１７０６８
６）、 キ）ホスト及びゲスト化合物が不溶の水媒体中、また
は、ホスト化合物が不溶でゲスト化合物が溶解するヘキ
サン中で撹はんする方法（Ｊ．ＣＨＥＭ．ＳＯＣ．，Ｃ
ＨＥＭ．ＣＯＭＭＵＮ．，１９９３、１２３８）等が知
られている。2. Description of the Related Art As a method for producing an inclusion compound, particularly an inclusion complex, using a host compound, in the case of a multi-molecular host, conventionally, a) a solution in which a guest compound is dissolved is added to a solution in which a host compound is dissolved. Method (JP-A-63-1320
1, JP-B-3-33121, JP-A-5-4978), a) Method of preparing a solution of guest and host compound (JP-A-60-222847, JP-A-62-142147, JP-A-5-163187, JP-A-6-163187). -72903), c) a method in which the guest compound is dissolved in an organic solvent in which the host compound is insoluble or sparingly soluble, and the host compound is added in the absence of water (JP-A-3-178906), and d) suspension water of the host compound. A method of adding and reacting an aqueous solution of a guest compound therein (JP-A-4-316564), E) a method of mixing a powder guest compound and a powder host compound (JP-A-63-35533), and a) a solid host compound and liquid Alternatively, a method of mixing with a liquid guest compound that is heated and melted (Japanese Patent Laid-Open No. 60-26038).
7, JP-A-62-160279, JP-A-1-16092
5, JP-A-4-150917, JP-A-5-17068
6), g) a method of stirring in an aqueous medium in which the host and guest compounds are insoluble, or in hexane in which the host compound is insoluble and the guest compound is dissolved (J. CHEM. SOC., C
HEM. COMMUN. , 1993, 1238) and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、前記ア）や
イ）の方法では、比較的良好な包接化合物が得られる反
面、ホストまたはゲスト化合物を溶解するために多量の
溶剤が必要であるため、大きな反応槽が必要となり、イ
ニシャルコストの増大、溶剤のコストや使用した溶剤の
処理コストの増大を招き、結果的に高価な包接化合物と
なる。また、溶解度を増加させるため高温に加熱したり
する必要があり危険性を伴う。エ）の方法は有機溶剤未
使用でありコスト面では好ましいが、ホスト化合物の溶
解度が比較的高い事が必要であり、限られた場合にしか
適用できない。オ）の場合は溶剤に起因するコスト問題
や危険性は排除できるが、混合が均一に行われ難く包接
効率が良好でない上、混合時に粉立ちが発生する可能性
がある。更に、カ）の方法は溶剤を必要とせずコスト的
に大変好ましいが、ホストまたはゲスト化合物が比較的
低温で融解しなければならず、通常の比較的高温で融点
を持つ化合物には使用できず限られた化合物のみにしか
適応できない。更に、包接体は塊で得られることが多
く、粉砕工程が必要となることがある。また、キ）の方
法は包接に長時間を要したり、ホスト及びゲスト化合物
を水に懸濁させる場合に分散助剤を必要とする。他方、
ウ）を含めホストまたはゲスト化合物どちらか一方のみ
が不溶である媒体を探索することは容易ではない。However, in the above methods a) and b), a relatively good clathrate compound can be obtained, but a large amount of solvent is required to dissolve the host or guest compound. However, a large reaction tank is required, the initial cost increases, the cost of the solvent and the cost of treating the used solvent increase, and as a result, an expensive inclusion compound is obtained. In addition, it is necessary to heat to a high temperature to increase the solubility, which is dangerous. The method (d) is preferable in terms of cost because it does not use an organic solvent, but it requires that the solubility of the host compound is relatively high, and is applicable only in a limited case. In the case of (e), the cost problem and danger due to the solvent can be eliminated, but it is difficult to mix uniformly, the inclusion efficiency is not good, and powdering may occur during mixing. Furthermore, the method (f) is very cost-effective since it does not require a solvent, but the host or guest compound must be melted at a relatively low temperature and cannot be used for a compound having a melting point at a relatively high temperature which is usually used. It can only be applied to a limited number of compounds. Furthermore, clathrates are often obtained in lumps and may require a crushing step. In addition, the method (g) requires a long time for inclusion and a dispersion aid when suspending the host and guest compounds in water. On the other hand,
It is not easy to search for a medium in which only one of the host compound and the guest compound is insoluble, including c).
【０００４】[0004]
【課題を解決するための手段】本発明者らは、この課題
を解決すべく鋭意検討を重ねた結果、固液不均一系、即
ち、ホスト化合物及びゲスト化合物を液体媒体中に溶解
及び分散させた系から包接化合物を効率的に得ることが
可能であることを見い出し、本発明を完成した。As a result of intensive studies to solve this problem, the present inventors have found that a solid-liquid heterogeneous system, that is, a host compound and a guest compound are dissolved and dispersed in a liquid medium. It was found that it is possible to efficiently obtain an inclusion compound from the above system and completed the present invention.
【０００５】詳しくは、ホスト化合物およびゲスト化合
物の一部を溶剤に溶解し、更に、残りの不溶解分を懸濁
または乳濁の分散状態で存在させておき、溶解している
ホスト化合物とゲスト化合物を反応させ、包接化反応で
消費した化合物を分散状態の化合物から溶解補充しつ
つ、最終的に包接化合物を製造するものである。更に詳
しくは、１）ホスト化合物及びゲスト化合物の両方が一
部溶剤に溶解している場合、２）ホスト化合物が一部溶
剤に溶解し、ゲスト化合物のほとんどまたはすべてが溶
剤に溶解している場合、３）ゲスト化合物が一部溶剤に
溶解し、ホスト化合物のほとんどまたはすべてが溶剤に
溶解している場合がある。両者ともに溶剤に当量溶解し
ていることが理想的であるが、両化合物が少量でも溶解
していればよい。溶解量としては添加量の１％〜５０％
で、多いほど好ましく、溶解量は多い程反応時間は少な
くて済む。Specifically, a part of the host compound and the guest compound is dissolved in a solvent, and the remaining insoluble matter is allowed to exist in a suspended or emulsified dispersed state, and the dissolved host compound and guest are dissolved. The compound is reacted and the compound consumed in the inclusion reaction is dissolved and replenished from the compound in the dispersed state to finally produce the inclusion compound. More specifically, 1) when both the host compound and the guest compound are partially dissolved in the solvent, and 2) when the host compound is partially dissolved in the solvent and most or all of the guest compound is dissolved in the solvent. 3) In some cases, the guest compound is partially dissolved in the solvent, and most or all of the host compound is dissolved in the solvent. It is ideal that both are dissolved in the solvent in an equivalent amount, but it is sufficient that both compounds are dissolved even in a small amount. Dissolved amount is 1% to 50% of the added amount
The larger the amount, the shorter the reaction time.
【０００６】本製造方法は、使用溶剤が少量で済むこと
から、反応槽を小型化でき、廃液が少量になり、廃液処
理も容易となり、大きな経済的効果をもたらすものであ
る。The present production method requires a small amount of solvent, so that the reaction tank can be downsized, the amount of waste liquid can be reduced, and the waste liquid can be easily treated.
【０００７】反応液相が単独溶剤や互いに溶けあう複数
の溶剤の均一混合系の場合、また、互いに溶け合わない
溶剤の多層系の場合はその内の少なくとも１層がホスト
及びゲスト化合物を溶解する必要があり、ホストおよび
ゲスト化合物の溶剤に対する溶解度は１％以上が好まし
い。溶解度が小さい場合は多量の溶剤を必要としたり、
包接速度が遅くなる。液相は均一系でも良いが、不均一
系、例えば水と有機溶剤とからなる多成分系でもよい。
一般に有機化合物は水に溶け難いため、ホストおよびゲ
スト化合物の易溶性有機溶剤と水の混合系が特に有用で
ある。In the case where the reaction liquid phase is a single solvent or a homogeneous mixed system of a plurality of solvents which are soluble in each other, or a multi-layer system of solvents which are insoluble in each other, at least one of them dissolves the host and guest compounds. The solubility of the host and guest compounds in the solvent is preferably 1% or more. If the solubility is low, a large amount of solvent is required,
Inclusion speed becomes slow. The liquid phase may be a homogeneous system or a heterogeneous system, for example, a multi-component system composed of water and an organic solvent.
In general, organic compounds are difficult to dissolve in water, so that a mixed system of a water-soluble organic solvent for the host and guest compounds and water is particularly useful.
【０００８】反応液相の例としては、ホスト化合物及び
ゲスト化合物に対し溶解度を持てばどのような溶剤でも
使用できる。単一溶剤では水、メタノール、エタノー
ル、プロパノール、ブタノール等のアルコール類、アセ
トン、メチルイソブチルケトン等のケトン類、酢酸エチ
ル等のエステル類、ブチルエーテル等のエーテル類、ト
ルエン、キシレン等の芳香族類に代表される通常の反応
溶剤が使用できる。As an example of the reaction liquid phase, any solvent can be used as long as it has solubility in the host compound and the guest compound. For a single solvent, use water, alcohols such as methanol, ethanol, propanol, butanol, ketones such as acetone and methyl isobutyl ketone, esters such as ethyl acetate, ethers such as butyl ether, and aromatics such as toluene and xylene. A typical reaction solvent represented can be used.
【０００９】混合溶剤の場合も前記溶剤の適当な組合せ
が使用できる。特に、生成する包接化合物が有機溶剤に
可溶な場合は、有機溶剤のほかに水を加え生成した包接
化合物を分離することが有効である。例えば水溶性のゲ
スト化合物と非水溶性でかつ有機溶剤に可溶なホスト化
合物による包接化合物の製造は水−メタノール、水−ア
セトン等の均一溶媒が、また、水−イソブタノール、水
−メチルイソブチルケトン、水−酢酸エチル、水−ブチ
ルエーテル、水−トルエン等の２層溶媒が有用である。
更に、有機溶剤を濃縮または留去し、ホスト及びゲスト
化合物の溶解量を下げることは収量を上げるのに有用で
ある。Also in the case of mixed solvents, suitable combinations of the abovementioned solvents can be used. In particular, when the generated clathrate compound is soluble in an organic solvent, it is effective to add water in addition to the organic solvent to separate the clathrate compound. For example, in the production of an inclusion compound by a water-soluble guest compound and a host compound which is water-insoluble and soluble in an organic solvent, a homogeneous solvent such as water-methanol or water-acetone can be used, or water-isobutanol or water-methyl. Bilayer solvents such as isobutyl ketone, water-ethyl acetate, water-butyl ether, water-toluene are useful.
Furthermore, it is useful to increase the yield by concentrating or distilling off the organic solvent to reduce the dissolved amount of the host and guest compounds.
【００１０】ホストおよびゲスト化合物としては、ホス
ト化合物およびゲスト化合物の溶解度が、両者からなる
包接化合物の溶解度よりも高ければどのような化合物で
も使用できる。As the host and guest compounds, any compound can be used as long as the solubility of the host compound and guest compound is higher than the solubility of the clathrate compound composed of both.
【００１１】例えばホスト化合物としては、１，１，
２，２−テトラキス（４−ヒドロキシフェニル）エタ
ン、１，１，２，２−テトラキス（３−メチル−４−ヒ
ドロキシフェニル）エタン、１，１，２，２−テトラキ
ス（３−クロロ−４−ヒドロキシフェニル）エタン、
１，１，２，２−テトラキス（３−フルオロ−４−ヒド
ロキシフェニル）エタン、１，１，２，２−テトラキス
（３−メトキシ−４−ヒドロキシフェニル）エタン、
１，１，２，２−テトラキス（３，５−ジメトキシ−４
−ヒドロキシフェニル）エタン、１，１，２，２−テト
ラキス（３−クロロ−５−メチル−４−ヒドロキシフェ
ニル）エタン、１，１，２，２−テトラキス（３−クロ
ロ−５−フェニル−４−ヒドロキシフェニル）エタン、
１，１，２，２−テトラキス〔４−ヒドロキシ−３−フ
ェニル）フェニル〕エタン、１，１−ビス（４−ヒドロ
キシフェニル）−２，２−ビス（３−メチル−４−ヒド
ロキシフェニル）エタン、１，１，３，３−テトラキス
（４−ヒドロキシフェニル）プロパン、１，１，３，３
−テトラキス（３−メチル−４−ヒドロキシフェニル）
プロパン、１，１，３，３−テトラキス（３−クロロ−
４−ヒドロキシフェニル）プロパン、１，１，３，３−
テトラキス（３−フルオロ−４−ヒドロキシフェニル）
プロパン、１，１，３，３−テトラキス（３−フェニル
−４−ヒドロキシフェニル）プロパン、１，１，４，４
−テトラキス（４−ヒドロキシフェニル）ブタンなど一
般式〔Ｉ〕で表される化合物、For example, as the host compound, 1,1,
2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-) Hydroxyphenyl) ethane,
1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane,
1,1,2,2-tetrakis (3,5-dimethoxy-4
-Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-4) -Hydroxyphenyl) ethane,
1,1,2,2-Tetrakis [4-hydroxy-3-phenyl) phenyl] ethane, 1,1-bis (4-hydroxyphenyl) -2,2-bis (3-methyl-4-hydroxyphenyl) ethane , 1,1,3,3-tetrakis (4-hydroxyphenyl) propane, 1,1,3,3
-Tetrakis (3-methyl-4-hydroxyphenyl)
Propane, 1,1,3,3-tetrakis (3-chloro-
4-hydroxyphenyl) propane, 1,1,3,3-
Tetrakis (3-fluoro-4-hydroxyphenyl)
Propane, 1,1,3,3-tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,4,4
-A compound represented by the general formula [I] such as tetrakis (4-hydroxyphenyl) butane,
【００１２】[0012]
【化１】 Embedded image
【００１３】２，４−ジヒドロキシベンゾフェノン、
４，４’−ジヒドロキシベンゾフェノン、２，２’，
４，４’−テトラヒドロキシベンゾフェノン、１，１，
２，２−テトラフェニルエタン−１，２−ジオール、
１，１−ビス（４−ヒドロキシフェニル）シクロヘキサ
ン、４，４’−スルホニルビスフェノール、２，２’−
メチレンビス（４−クロロフェノール）、２，５−ビス
（２，４−ジメチルフェニル）ヒドロキノン、２，５−
ジ−ｔｅｒｔ−ブチルヒドロキノン、１，１−ビ−２−
ナフトール、４，４’−スルホニルビスフェノール、デ
オキシコール酸などを挙げることができる。2,4-dihydroxybenzophenone,
4,4'-dihydroxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 1,1,
2,2-tetraphenylethane-1,2-diol,
1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonylbisphenol, 2,2′-
Methylenebis (4-chlorophenol), 2,5-bis (2,4-dimethylphenyl) hydroquinone, 2,5-
Di-tert-butylhydroquinone, 1,1-bi-2-
Examples thereof include naphthol, 4,4′-sulfonylbisphenol, deoxycholic acid and the like.
【００１４】ゲスト化合物としては、５−クロロ−２−
メチル−４−イソチアゾリン−３−オン、１，２−ベン
ズイソチアゾリン−３−オン、２，３，５，６−テトラ
クロロ−４−（メチルスルフォニル）ピリジン、４，５
−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−
３−オン、２−ｎ−オクチル−４−イソチアゾリン−３
−オン、２−メトキシカルボニルベンズイミダゾール、
４、５−ジクロロ−１、２−ジチオラン−３−オン、５
−クロロ−４−フェニル−１、２−ジチオラン−３−オ
ン、エチルアルコール、チモール、シネオール、ヒノキ
チオール、メントール、ボルネオール、メントン、カル
ボン、オイゲノール、テルピネオール、シトラール、ゲ
ラニオール、Ｎ1 −〔（６−クロロ−３−ピリジル）メ
チル〕−Ｎ2 −シアノ−Ｎ1 −メチルアセタミジン、
Ｎ，Ｎ−ジエチル−ｍ−トルアミド、α−ブロムシンナ
ムアルデヒド等があげられる。As the guest compound, 5-chloro-2-
Methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 4,5
-Dichloro-2-n-octyl-4-isothiazoline-
3-one, 2-n-octyl-4-isothiazoline-3
-One, 2-methoxycarbonylbenzimidazole,
4,5-dichloro-1,2-dithiolan-3-one, 5
-Chloro-4-phenyl-1,2-dithiolan-3-one, ethyl alcohol, thymol, cineol, hinokitiol, menthol, borneol, menthone, carvone, eugenol, terpineol, citral, geraniol, N 1 -[(6-chloro -3-Pyridyl) methyl] -N 2 -cyano-N 1 -methylacetamidine,
Examples thereof include N, N-diethyl-m-toluamide and α-bromocinnamaldehyde.
【００１５】本製造法の一般的な工程は、液温や溶剤量
を調節した溶剤中にホスト化合物またはゲスト化合物の
両方またはどちらかが分散状態で反応すれば良く、両化
合物を一度に仕込む方法、両化合物を徐々に添加する方
法、一方の化合物に他方を添加していく方法等、化合物
に応じ任意の方法をとることが出来る。反応時に、加
熱、冷却することも有用である。生成した包接化合物は
反応液から分離、必要に応じ洗浄し、乾燥する。The general process of the present production method is to react both the host compound and / or the guest compound in a dispersed state in a solvent in which the liquid temperature and the amount of solvent are adjusted, and to charge both compounds at once. Any method can be used depending on the compound, such as a method of gradually adding both compounds and a method of adding the other to one compound. It is also useful to heat and cool during the reaction. The produced clathrate compound is separated from the reaction solution, washed if necessary, and dried.
【００１６】[0016]
【実施例】次にホスト化合物として１，１，２，２−テ
トラキス（４−ヒドロキシフェニル）エタン（ＴＥＰと
略）、ゲスト化合物として５−クロロ−２−メチル−４
−イソチアゾリン−３−オン（ＣＭＩと略）の包接物に
関する本発明の実施例を示すが、本発明はこれらの例に
限定されるものではない。尚、ＣＭＩはＴＥＰの２倍モ
ル添加し、理論的包接比は２．０である。表１にＴＥＰ
の各種溶剤に対する溶解度をしめした。EXAMPLES Next, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (abbreviated as TEP) was used as a host compound, and 5-chloro-2-methyl-4 was used as a guest compound.
-Examples of the present invention relating to the inclusion compound of -isothiazolin-3-one (abbreviated as CMI) are shown, but the present invention is not limited to these examples. In addition, CMI is added twice the molar amount of TEP, and the theoretical inclusion ratio is 2.0. Table 1 shows TEP
Solubility in various solvents was shown.
【００１７】[0017]
【表１】 [Table 1]
【００１８】実施例−１ 水−イソブタノール３層系 蛇管冷却器、温度計、撹はん器を備えた１リットルフラ
スコにイソブタノール５０グラム、ＴＥＰ５０グラムを
入れ６５℃に加温する（この時には一部溶解および不溶
解ＴＥＰが共存する）。これにケーソンＷＴ（ローム・
アンド・ハース社製：ＣＭＩを約１０％含有する水溶
液）３６０グラムを２０分で滴下、熟成２時間、約３時
間で５℃まで徐冷し、固形物を濾過、減圧乾燥した。Example 1 Water-isobutanol three-layer system In a 1 liter flask equipped with a conical condenser, thermometer and stirrer, 50 g of isobutanol and 50 g of TEP were placed and heated to 65 ° C. Partially soluble and insoluble TEP coexist). Caisson WT (ROHM
360 g of an aqueous solution containing CMI of about 10%) was added dropwise in 20 minutes, and the mixture was gradually cooled to 5 ° C. in 2 hours of aging and 3 hours of aging. The solid matter was filtered and dried under reduced pressure.
【００１９】実施例−２ 水−酢エチ３層系 蛇管冷却器、温度計、撹はん器を備えた１リットルのフ
ラスコに酢酸エチル５０グラムとＴＥＰ５０グラムを入
れ６５℃に加温する（この時には一部溶解および不溶解
ＴＥＰが共存する）。これにケーソンＷＴ（ローム・ア
ンド・ハース社製：ＣＭＩを約１０％含有する水溶液）
３６０グラムを２０分で滴下、約２時間熟成し、５℃ま
で３時間かけ徐冷し、固形物を濾過、減圧乾燥した。Example 2 Water-Ethyl Acetate 3-Layer System 50 g of ethyl acetate and 50 g of TEP were placed in a 1 liter flask equipped with a serpentine condenser, a thermometer and a stirrer and heated to 65 ° C. Sometimes some dissolved and insoluble TEP coexist). Caisson WT (Rohm and Haas Co .: an aqueous solution containing about 10% CMI)
360 g was dropped in 20 minutes, aged for about 2 hours, gradually cooled to 5 ° C. over 3 hours, and the solid matter was filtered and dried under reduced pressure.
【００２０】実施例−３ 水−酢エチ３層系（濃縮） 蛇管冷却器、温度計、撹はん器を備えた１リットルのフ
ラスコに酢酸エチル５０グラムとＴＥＰ５０グラムを入
れ６５℃に加温する（この時には一部溶解および不溶解
ＴＥＰが共存する）。これにケーソンＷＴ（ローム・ア
ンド・ハース社製：ＣＭＩを約１０％含有する水溶液）
３６０グラムを２０分で滴下、約２時間熟成し、酢酸エ
チルを減圧下、６０℃で留去する。次に５℃まで３時間
かけ徐冷し、固形物を濾過、減圧乾燥した。Example 3 Water-Ethyl acetate 3-layer system (concentration) 50 g of ethyl acetate and 50 g of TEP were placed in a 1-liter flask equipped with a spiral condenser, a thermometer and a stirrer and heated to 65 ° C. (At this time, partially dissolved and insoluble TEP coexist). Caisson WT (Rohm and Haas Co .: an aqueous solution containing about 10% CMI)
360 g is added dropwise over 20 minutes and aged for about 2 hours, and ethyl acetate is distilled off under reduced pressure at 60 ° C. Next, the mixture was gradually cooled to 5 ° C. over 3 hours, and the solid substance was filtered and dried under reduced pressure.
【００２１】実施例−４ 水−メチルイソブチルケトン３層系 蛇管冷却器、温度計、撹はん器を備えた１リットルのフ
ラスコにメチルイソブチルケトン１００グラム、ＴＥＰ
５０グラムを入れ６５℃に加温する（この時には一部溶
解および不溶解ＴＥＰが共存する）。これにケーソンＷ
Ｔ（ローム・アンド・ハース社製：ＣＭＩを約１０％含
有する水溶液）３６０グラムを２０分で滴下、２時間熟
成、３時間で５℃まで徐冷し、固形物を濾過、減圧乾燥
した。Example 4 Water-Methylisobutylketone Three-Layer System 100 g of methylisobutylketone and TEP were placed in a 1-liter flask equipped with a spiral condenser, a thermometer, and a stirrer.
Add 50 g and heat to 65 ° C (at this time, partially dissolved and insoluble TEP coexist). Caisson w
360 g of T (manufactured by Rohm and Haas: an aqueous solution containing about 10% of CMI) was added dropwise over 20 minutes, aged for 2 hours, gradually cooled to 5 ° C. over 3 hours, and the solid matter was filtered and dried under reduced pressure.
【００２２】比較例−１ 水−メタノール均一系 蛇管冷却器、温度計、撹はん器を備えた２リットルのフ
ラスコにメタノール５５０グラム（メタノールの量がこ
れより少ないとＴＥＰが全量溶解しない）とＴＥＰ１０
０グラムを入れ、６５℃に加温しＴＥＰを溶解する。こ
れにケーソンＷＴ（ローム・アンド・ハース社製：ＣＭ
Ｉを約１０％含有する水溶液）７６０グラムを２５分で
滴下、１時間熟成した後、撹はんしながら１時間空冷
し、更に１時間水冷し２０℃まで冷却し、固形物を減圧
濾過した。Comparative Example-1 Water-methanol homogeneous system In a 2 liter flask equipped with a coil condenser, a thermometer and a stirrer, 550 g of methanol (if the amount of methanol is less than this, the total amount of TEP is not dissolved). TEP10
Add 0 g and heat to 65 ° C. to dissolve TEP. Caisson WT (Rohm and Haas Company: CM
760 g of an aqueous solution containing about 10% of I) was added dropwise over 25 minutes, aged for 1 hour, air-cooled for 1 hour with stirring, further water-cooled for 1 hour and cooled to 20 ° C., and the solid matter was filtered under reduced pressure. .
【００２３】比較例−２ 水−不均一系 蛇管冷却器、温度計、撹はん器を備えた２リットルのフ
ラスコに水５００グラムとＴＥＰ５０グラムを入れ６５
℃に加温する（この時ＴＥＰは殆ど溶解しない）。これ
にケーソンＷＴ（ローム・アンド・ハース社製：ＣＭＩ
を約１０％含有する水溶液）３６０グラムを２０分で滴
下、約２時間熟成し、５℃まで３時間かけ徐冷し、固形
物を濾過、減圧乾燥した。Comparative Example 2 Water-Heterogeneous system 500 g of water and 50 g of TEP were placed in a 2 liter flask equipped with a coil condenser, a thermometer and a stirrer.
Heat to ℃ (TEP hardly dissolves at this time). Caisson WT (Rohm and Haas Company: CMI
(10% aqueous solution containing about 10%) was added dropwise over 20 minutes, aged for about 2 hours, gradually cooled to 5 ° C. over 3 hours, and the solid matter was filtered and dried under reduced pressure.
【００２４】表２に実施例１〜４と比較例１〜２の結果
をまとめて示した。Table 2 collectively shows the results of Examples 1 to 4 and Comparative Examples 1 and 2.
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】本製造方法は、使用溶剤が少量で済むこ
とから、反応槽を小型化でき、廃液が少量になり、廃液
処理も容易になる効率の良い製法であり、製造された包
接化合物はホスト化合物及びゲスト化合物両者を完全溶
解した後、包接化合物を調製したものと比較しても品質
的に遜色のないものである。EFFECTS OF THE INVENTION Since this manufacturing method requires only a small amount of solvent, the reaction tank can be downsized, the amount of waste liquid can be reduced, and the waste liquid can be easily treated. The compound is comparable in quality to the one prepared by preparing the clathrate compound after completely dissolving both the host compound and the guest compound.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 杉本 義昭 富山県高岡市向野本町300 日本曹達株式 会社高岡工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiaki Sugimoto 300 Mukaihoncho, Takaoka City, Toyama Prefecture Inside the Takaoka Plant of Nippon Soda Co., Ltd.
Claims (4)
体中に一部溶解した系から包接化合物を得ることを特徴
とする包接化合物の製造方法。1. A method for producing an inclusion compound, which comprises obtaining an inclusion compound from a system in which a host compound or a guest compound is partially dissolved in a liquid medium.
ハロゲン原子、低級アルコキシ基、フェニル基で置換さ
れていてもよいフェノール性水酸基を２個以上含む化合
物、２，５−ビス（２，４−ジメチルフェニル）ハイド
ロキノン、２，５−ジ−ｔｅｒｔ−ブチルハイドロキノ
ン、１，１−ビ−２−ナフトール、４，４’−スルホニ
ルビスフェノール、デオキシコール酸から選ばれる１種
であることを特徴とする請求項１に記載の包接化合物の
製造方法。2. A host compound is a lower alkyl group in the molecule,
Halogen atom, lower alkoxy group, compound containing two or more phenolic hydroxyl groups which may be substituted with phenyl group, 2,5-bis (2,4-dimethylphenyl) hydroquinone, 2,5-di-tert-butyl The method for producing an inclusion compound according to claim 1, which is one kind selected from hydroquinone, 1,1-bi-2-naphthol, 4,4′-sulfonylbisphenol, and deoxycholic acid.
ルアミド、α−ブロムシンナムアルデヒド、５−クロロ
−２−メチル−４−イソチアゾリン−３−オン、４，５
−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−
３−オン、２−ｎ−オクチル−４−イソチアゾリン−３
−オン、シネオール、ヒノキチオールから選ばれる１種
または２種以上であることを特徴とする請求項１に記載
の包接化合物の製造方法。3. The guest compound is N, N-diethyl-m-toluamide, α-bromocinnamaldehyde, 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5.
-Dichloro-2-n-octyl-4-isothiazoline-
3-one, 2-n-octyl-4-isothiazoline-3
The method for producing an inclusion compound according to claim 1, wherein the inclusion compound is one kind or two or more kinds selected from -one, cineol, and hinokitiol.
ル、ブタノール、アセトン、メチルイソブチルケトン、
ブチルエーテル、酢酸エチル、トルエン、キシレンから
選ばれる１種または２種以上であることを特徴とする請
求項１に記載の包接化合物の製造方法。4. The liquid medium is water, methanol, propanol, butanol, acetone, methyl isobutyl ketone,
It is 1 type (s) or 2 or more types selected from butyl ether, ethyl acetate, toluene, and xylene, The manufacturing method of the inclusion compound of Claim 1 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34028094A JP3839859B2 (en) | 1994-12-28 | 1994-12-28 | Method for producing inclusion compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34028094A JP3839859B2 (en) | 1994-12-28 | 1994-12-28 | Method for producing inclusion compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08183744A true JPH08183744A (en) | 1996-07-16 |
| JP3839859B2 JP3839859B2 (en) | 2006-11-01 |
Family
ID=18335432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34028094A Expired - Lifetime JP3839859B2 (en) | 1994-12-28 | 1994-12-28 | Method for producing inclusion compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3839859B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016656A1 (en) * | 1997-09-02 | 2000-07-05 | Nippon Soda Co., Ltd. | Molecular compounds containing phenol derivatives as constituent |
| EP1428831A4 (en) * | 2002-06-19 | 2006-09-20 | Kurita Water Ind Ltd | Method of storing hydrogen, hydrogen inclusion compound and process for producing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2149364A1 (en) | 2008-07-24 | 2010-02-03 | Rohm and Haas Company | Method for reducing odor in personal care products |
-
1994
- 1994-12-28 JP JP34028094A patent/JP3839859B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016656A1 (en) * | 1997-09-02 | 2000-07-05 | Nippon Soda Co., Ltd. | Molecular compounds containing phenol derivatives as constituent |
| EP1016656A4 (en) * | 1997-09-02 | 2004-12-29 | Nippon Soda Co | Molecular compounds containing phenol derivatives as constituent |
| EP1428831A4 (en) * | 2002-06-19 | 2006-09-20 | Kurita Water Ind Ltd | Method of storing hydrogen, hydrogen inclusion compound and process for producing the same |
| JP2009203159A (en) * | 2002-06-19 | 2009-09-10 | Kurita Water Ind Ltd | Hydrogen clathrate compound and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3839859B2 (en) | 2006-11-01 |
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