JP3109116B2 - Clathrate compound - Google Patents
Clathrate compoundInfo
- Publication number
- JP3109116B2 JP3109116B2 JP03065940A JP6594091A JP3109116B2 JP 3109116 B2 JP3109116 B2 JP 3109116B2 JP 03065940 A JP03065940 A JP 03065940A JP 6594091 A JP6594091 A JP 6594091A JP 3109116 B2 JP3109116 B2 JP 3109116B2
- Authority
- JP
- Japan
- Prior art keywords
- cmi
- compound
- clathrate
- present
- clathrate compound
- 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
Links
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は包接化合物に係り、特に
工業用殺菌剤の有効成分である５−クロロ−２−メチル
−４−イソチアゾリン−３−オンの殺菌剤成分の長期安
定化、粉末化を可能とし、かつ、皮膚刺激性を緩和する
ことにより取り扱い性の向上、使用形態の拡大を図る包
接化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to clathrate compounds, and more particularly to the long-term stabilization of the fungicide component of 5-chloro-2-methyl-4-isothiazolin-3-one, which is an active ingredient of industrial fungicides. The present invention relates to a clathrate compound which can be powdered, and which improves the handleability by relaxing skin irritation and expands the use form.
【０００２】[0002]
【従来の技術】各種工場施設の冷却水系或は紙パルプ抄
造系等の水系においては、様々な菌類又は動植物類のス
ライムが付着し、様々な障害を引き起こしている。2. Description of the Related Art In a water system such as a cooling water system or a paper pulp papermaking system of various factory facilities, slime of various fungi or animals and plants adheres and causes various obstacles.
【０００３】従来、スライム等による障害を防止するた
めには、その処理法が比較的簡便なこと、安価であるこ
とから、抗菌剤（スライムコントロール剤）が一般に使
用されている。しかして、抗菌剤として特に下記（II）
式で示される５−クロロ−２−メチル−４−イソチアゾ
リン−３−オン（以下「ＣＭＩ」と略称する。）が抗菌
力に優れていることから、冷却水系用、紙パルプ用、水
泳プール用等各種水系用スライムコントロール剤、殺菌
剤、殺藻剤、殺かび剤として広く使用されている。[0003] Conventionally, in order to prevent obstacles due to slime and the like, antibacterial agents (slime control agents) are generally used because their treatment methods are relatively simple and inexpensive. In particular, the following (II)
Since 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as “CMI”) represented by the formula has excellent antibacterial activity, it is used for cooling water systems, paper pulp, and swimming pools. Widely used as slime control agents for various water systems, fungicides, algicides, and fungicides.
【０００４】[0004]
【化２】 Embedded image
【０００５】[0005]
【発明が解決しようとする課題】ＣＭＩは非常に有効な
工業用殺菌剤成分であるが、次のような欠点を有し、取
り扱い性、保存性、使用形態等の面で問題があった。
室温、空気中にて非常に不安定である。皮膚刺激性が
極めて強い。融点５４〜５５℃の低融点化合物である
ため、各種の成型が困難である。Although CMI is a very effective industrial bactericide component, it has the following drawbacks, and has problems in handling, preservability, use form and the like.
Very unstable at room temperature and in air. Extremely irritating to the skin. Since it is a low melting point compound having a melting point of 54 to 55 ° C., various types of molding are difficult.
【０００６】本発明は上記従来の問題点を解決し、ＣＭ
Ｉの長期安定性、取り扱い性の改善に有効で、また、成
型による使用形態の拡大が図れる包接化合物を提供する
ことを目的とする。[0006] The present invention solves the above-mentioned conventional problems and provides a CM.
It is an object of the present invention to provide an inclusion compound which is effective for improving the long-term stability and handleability of I and can expand the use form by molding.
【０００７】[0007]
【課題を解決するための手段】本発明の包接化合物は、
ＣＭＩと、下記構造式（Ｉ）で示されるジベンゾチアジ
ルジスルフィドとからなることを特徴とする。The clathrate compound of the present invention comprises:
CMI and dibenzothiazidione represented by the following structural formula (I)
Characterized by consisting of rudisulfide .
【０００８】[0008]
【化３】 Embedded image
【０００９】即ち、本発明の包接化合物は、ＣＭＩをゲ
スト化合物、上記ジベンゾチアジルジスルフィドをホス
ト化合物として、ゲスト化合物をホスト化合物で包接し
てなるものである。[0009] That is, inclusion compound of the present invention, gate <br/> strike compound CM I, the dibenzothiazyl disulfide as a host compound is made in contact with the packaging of the guest compound in the host compound.
【００１０】以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail .
【００１１】このようなＣＭＩとジベンゾチアジルジス
ルフィドとからなる本発明の包接化合物は、溶媒中もし
くは無溶媒反応にて容易に製造することができる。[0011] Such CMI and dibenzothiazyldis
The clathrate compound of the present invention comprising sulfide can be easily produced in a solvent or by a solventless reaction.
【００１２】溶媒を用いる場合には、メタノール、エタ
ノール、アセトン等の通常の水可溶性溶媒にホスト化合
物を溶解させた溶液と、ＣＭＩあるいはこれに更に不純
物等を含む混合物とを混合して反応させる。これによ
り、包接化合物が固形物として析出するので、これを常
法により濾過分離して目的とする包接化合物を得る。[0012] When a solvent is used, methanol, ethanol, and the solution obtained by dissolving the host compound in normal water-soluble solvents such as acetone, CM I Oh Rui by mixing the mixture containing it to further impurities Let react. As a result, the clathrate compound precipitates as a solid, and is separated by filtration by a conventional method to obtain a target clathrate compound.
【００１３】無溶媒反応の場合には、ホスト化合物を直
接ゲスト化合物であるＣＭＩを溶解した液中に添加して
混合、撹拌する。用いる液は、必ずしもゲスト化合物と
なるＣＭＩのみを含むものである必要はなく、前記溶媒
反応の場合と同様、ＣＭＩと不純物等を含むものであっ
ても良い。In the case of a solventless reaction, a host compound is directly added to a solution in which CMI as a guest compound is dissolved, and mixed and stirred. The liquid to be used does not necessarily need to contain only CMI as a guest compound, and may contain CMI and impurities as in the case of the solvent reaction.
【００１４】反応終了後、包接化合物は通常固形物とし
て得られるので、これを水層と分離し、水洗、乾燥し
て、目的とする包接化合物を得ることができる。After completion of the reaction, since the clathrate is usually obtained as a solid, it is separated from the aqueous layer, washed with water and dried to obtain the desired clathrate.
【００１５】このようにして得られる本発明の包接化合
物は、通常は粉末状の固体であり、打錠等の成型も容易
である。またＣＭＩが包接されているので、毒性が低
く、取り扱いが容易である。しかも、長期安定性に優
れ、保存中に抗菌活性が低下することも防止される。The thus obtained clathrate compound of the present invention is usually a powdery solid, and is easy to mold such as tableting. In addition, since CMI is included, it has low toxicity and is easy to handle. Moreover, it has excellent long-term stability and prevents the antibacterial activity from being reduced during storage.
【００１６】[0016]
【作用】ＣＭＩはジベンゾチアジルジスルフィドのホス
ト化合物との包接化合物とされることにより、固体状態
となり、各種成型が可能となる。また、ＣＭＩは包接さ
れることにより、その毒性、皮膚刺激性等が低減され
る。しかも、長期安定性が付与され、保存中に抗菌活性
が低下することも防止される。The CMI is in the form of an inclusion compound of dibenzothiazyl disulfide and a host compound, so that it is in a solid state and can be molded in various forms. The inclusion of CMI reduces its toxicity, skin irritation and the like. In addition, long-term stability is imparted, and a decrease in antibacterial activity during storage is prevented.
【００１７】[0017]
【実施例】以下に本発明を実施例を挙げて更に具体的に
説明するが、本発明はその要旨を超えない限り以下の実
施例に限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to the following Examples without departing from the scope of the invention.
【００１８】実施例１ ＣＭＩを主成分として含む水溶性殺菌剤水溶液（殺菌剤
濃度１０．４重量％）をＣＨ２Ｃｌ２を用いて抽出し、
その後、ＣＨ２Ｃｌ２を留去することにより、ＣＭＩを
約９０重量％含むＣＭＩ粗結晶を得た。このＣＭＩ粗結
晶を０．５ｇサンプルビンに採り、６０℃湯浴中で溶解
させ、これに前記構造式（Ｉ）で示されるベンゾチアジ
ルジスルフィドをＣＭＩ／ベンゾチアジルジスルフィド
＝１／１（モル比）となるように添加し、２分間スパー
テルで撹拌後、室温に冷却したところ、包接化合物が得
られた。Example 1 A water-soluble bactericide aqueous solution containing a CMI as a main component (a bactericide concentration of 10.4% by weight) was extracted with CH 2 Cl 2 ,
Then, by distilling off the CH 2 Cl 2, to give a CMI crude crystals containing about 90% by weight of CMI. 0.5 g of this CMI crude crystal is taken in a sample bottle and dissolved in a 60 ° C. water bath, and the benzothiazyl disulfide represented by the above structural formula (I) is mixed with CMI / benzothiazyl disulfide = 1/1 (mol Ratio), stirred with a spatula for 2 minutes, and cooled to room temperature to obtain an inclusion compound.
【００１９】この包接化合物の融点は１７０〜１７３℃
であり、ＣＭＩの融点５４〜５５℃よりも高くなってい
ることが確認された。The melting point of this clathrate compound is 170-173 ° C.
It was confirmed that the melting point of CMI was higher than 54 to 55 ° C.
【００２０】実施例２ 実施例１で得られた包接化合物とＣＭＩ単独とについ
て、室温、空気中での安定性及び皮膚刺激性を調べた。
安定性は、所定日数経過後のＣＭＩ残留率で調べた。Example 2 The clathrate compound obtained in Example 1 and CMI alone were examined for room temperature, air stability and skin irritation.
The stability was determined by the CMI residual ratio after a predetermined number of days had passed.
【００２１】結果を表１に示す。The results are shown in Table 1.
【００２２】表１より、本発明の包接化合物では約１ケ
月経過後も約９５重量％のＣＭＩが残留し、長期安定性
に優れ、また、皮膚刺激性もなく、取り扱い性に優れる
ことが明らかである。From Table 1, it can be seen that the clathrate of the present invention retains about 95% by weight of CMI even after about one month, has excellent long-term stability, has no skin irritation, and has excellent handleability. it is obvious.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】以上詳述した通り、本発明の包接化合物
は、ＣＭＩをジベンゾチアジルジスルフィドにより包接
したものであり、 化学的に不安定なＣＭＩを長期安
定化することができ、抗菌活性の低下が防止される。
ＣＭＩの毒性、皮膚刺激性等が低減される。これによ
り、作業環境が改良され、安全性が向上される。 固
体粉末状とすることができるため、粉砕微粉化、打錠成
型等の成型が可能であり、取り扱い性を改善することが
できる。等の優れた効果を有し、工業的に極めて有用で
ある。As described in detail above, the clathrate compound of the present invention is a compound in which CMI is clathrated with dibenzothiazyl disulfide , and can stabilize chemically unstable CMI for a long time, A decrease in activity is prevented.
The toxicity and skin irritation of CMI are reduced. Thereby, the working environment is improved and safety is improved. Since it can be made into a solid powder, it can be pulverized and pulverized, and can be formed by tableting and the like, and handleability can be improved. Etc., and are extremely useful industrially.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ａ０１Ｎ 43/80 １０２ Ｃ０２Ｆ 1/50 Ｃ０２Ｆ 1/50 Ｃ０７Ｄ 275/02 (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 25/22 A01N 25/32 A01N 43/78 101 A01N 43/80 102 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 identification code FI A01N 43/80 102 C02F 1/50 C02F 1/50 C07D 275/02 (58) Investigated field (Int.Cl. 7 , DB name) ) A01N 25/22 A01N 25/32 A01N 43/78 101 A01N 43/80 102 CA (STN) REGISTRY (STN)
Claims (1)
ゾリン−３−オンと、下記構造式（Ｉ）で示されるジベ
ンゾチアジルジスルフィドとからなる包接化合物。 【化１】 (1) 5-chloro-2-methyl-4-isothia
-3-one and, Jibe represented by the following structural formula (I)
Inclusion compound consisting of nzothiazyl disulfide . Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03065940A JP3109116B2 (en) | 1991-03-29 | 1991-03-29 | Clathrate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03065940A JP3109116B2 (en) | 1991-03-29 | 1991-03-29 | Clathrate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04300803A JPH04300803A (en) | 1992-10-23 |
| JP3109116B2 true JP3109116B2 (en) | 2000-11-13 |
Family
ID=13301468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03065940A Expired - Lifetime JP3109116B2 (en) | 1991-03-29 | 1991-03-29 | Clathrate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3109116B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5725806A (en) * | 1995-12-05 | 1998-03-10 | Rohm And Haas Company | Disulfide stabilizers for 3-isothiazolones |
-
1991
- 1991-03-29 JP JP03065940A patent/JP3109116B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04300803A (en) | 1992-10-23 |
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