JP3679818B2 - Underwater biofouling agent - Google Patents

Description

【０００７】
さらに本発明は、５, ６−ジクロログラミン、５−クロロ−２−メチルグラミン、５−ブロモ−２−メチルグラミン、１, ２−ジメチル−６−ブロモグラミン、５, ６−ジクロロ−１−メチルグラミンより選ばれた一種又はそれ以上を有効成分として含有する事を特徴とする水中付着生物防汚剤を提供するものである。
なお、以下の記載においては必要により化合物名を下記のように略記する。
５, ６−ジクロログラミン：（化合物１）
５−クロロ−２−メチルグラミン： (化合物２）
５−ブロモ−２−メチルグラミン：（化合物３）
１, ２−ジメチル−６−ブロモグラミン：（化合物４）
５, ６−ジクロロ−１−メチルグラミン：（化合物５）
以下、本発明ついて詳細に説明する。
【０００８】
本発明の水中付着生物防汚剤の有効成分として使用する化合物１〜５（以下、これらを単に「本剤化合物」と記載することがある。）は、例えば下記の方法により製造する事が可能である。
５, ６−ジクロログラミンは、５，６−ジクロロインドリンをジクロロジシアノキノン等で処理して５，６−ジクロロインドールとしたのち更に、ジメチルアミンおよびホルムアルデヒドを用いてマンニッヒ反応する事により製造できる。
【０００９】
５−クロロ−２−メチルグラミンは、５−クロロ−２−メチルインドリンをジクロロジシアノキノン等で処理して得た５−クロロ−２−メチルインドールを更に、ジメチルアミンおよびホルムアルデヒドを用いてマンニッヒ反応する事により製造できる。
５−ブロモ−２−メチルグラミンは、５−ブロモ−２−メチルインドリンをジクロロジシアノキノン等で処理して得た５−ブロモ−２−メチルインドールを更に、ジメチルアミンおよびホルムアルデヒドを用いてマンニッヒ反応する事により製造できる。
【００１０】
１, ２−ジメチル−６−ブロモグラミンは、５−クロロ−２−メチルインドリンをジクロロジシアノキノン等で処理して得た５−クロロ−２−メチルインドールを、ヨウ化メチル等でＮ−メチル化したのち更に、ジメチルアミンおよびホルムアルデヒドを用いてマンニッヒ反応する事により製造できる。
５, ６−ジクロロ−１−メチルグラミンは、５，６−ジクロロインドリンをジクロロジシアノキノン等で処理して得た５，６−ジクロロインドールを、ヨウ化メチル等でＮ−メチル化したのち更に、ジメチルアミンおよびホルムアルデヒドを用いてマンニッヒ反応する事により製造できる。なお、この化合物は新規化合物である。
【００１１】
本発明の水中付着生物防汚剤は、本剤化合物それ自体をそのまま用いることもできるが、目的や対象に応じて例えば塗料、溶液、乳剤、あるいはペレット、フレーク等の適当な剤型に本剤化合物を製剤することにより、例えば船舶の船底部、漁網、ブイ等の海中に置かれる設備、ダムの付属設備等の水中構築物、火力発電所の復水器冷却用水や石油化学工業の熱交換器冷却用水の取水路等の水中付着生物防汚が必要とされる広範な対象に使用できる。本発明の水中付着生物防汚剤を船舶の船底部および漁網、ブイ等の海中に置かれた設備、ダムの附属設備等の水中構築物及び火力発電所の復水器冷却用水あるいは石油化学工業の熱交換器冷却用水の取水路等の常時海水と接触する部分に使用する場合、通常は本剤化合物を塗料に製剤して使用するが、所望により、乳剤の形態で取水路の中へ添加しても良い。また本化合物を親水性樹脂、界面活性剤等と熱溶融成形または混合圧縮成形等の方法によりペレット状に成形し、海水を利用する冷却水系に設置しても良い。
【００１２】
本剤化合物を塗料として製剤する場合は、本剤化合物を塗膜形成剤、必要に応じて可塑剤、着色顔料、体質顔料、その他塗料調製に慣用の成分を配合して攪拌機、あるいは三本ロール、サンドミル等慣用の分散機を使用し塗料化すれば良い。すなわち、例えば本剤化合物と、トルエン、キシレン、クメン、ナフサ等の芳香族系、プロパノール等のアルコール系、あるいはメチルイソブチルケトン等のケトン系等の溶剤、油ワニス、アクリル樹脂等の合成樹脂、合成ゴム、ロジン等の塗膜形成剤、必要に応じ染料、ジオクチルフタレート（ＤＯＰ）、塩素化パラフィン等の可塑剤、弁柄等の着色顔料、あるいは硫酸バリウム、タクル等の体質顔料等を適宜配合することにより塗料に製剤できる。また、本剤化合物は水、例えば前記芳香族炭化水素等の水に混和しない溶媒、および陰イオン系、非イオン系、陽イオン系等の公知の界面活性剤を配合して乳剤に製剤できる。さらに例えば常温で固体状のポリエチレングリコール等の親水性樹脂を基剤として、本剤化合物および必要に応じ可塑剤、界面活性剤等を構成成分として配合し、溶融成型あるいは圧縮成型等の方法でペレットやフレークとすることもできる。製剤する場合の本剤化合物の配合量は、目的、剤型、使用方法等の条件により適宜選ばれ、本剤化合物が製剤化を妨害しない限りにおいてその配合量に制限はないが、本剤化合物を例えば塗料、溶液、乳剤等にする場合、通常は１〜40重量％、好ましくは３〜20重量％の割合で配合すればよく、また、ペレット等にする場合、通常は30〜95重量％、好ましくは50〜90重量％の割合で配合すればよい。その他の構成成分は各製剤において一般的に用いられるものを用いてよく、その種類、組合せ、配合量等は本明細書中の例示にとどまらず所望の製剤物性等に合わせて適宜、広い範囲で変更しうる。
【００１３】
本発明の水中付着生物防汚剤はその使用場所や目的、剤型に応じ、塗布、含浸、水中添加、水中設置等の通常慣用の手法を適宜選択することにより使用できる。すなわち、本発明の水中付着生物防汚剤を例えば塗料とした場合は船底、漁網、水中構築物、取水路等に塗布等の方法で使用でき、対象が漁網の場合には、塗料、または溶液として製剤した本発明の水中付着生物防汚剤に漁網を浸漬し、被覆および／または含浸させ使用することも効果的な使用法として例示できる。また、対象が取水路である場合には溶液あるいは乳剤としたものを水中添加する方法や、ペレットあるいはフレークとしたものを例えば吊り下げ、張り付け等、実際の使用状況に応じて適宜選択される公知の設置方法で使用する方法も例示できる。さらに例えば漁網等に使用されるロープあるいは繊維素材の製造段階で本剤化合物を組み込み、ロープあるいは繊維素材自体に水中付着生物防汚性能を付与する等の、前記例示以外の剤型および方法で使用することもできる。
【００１４】
また、本発明の水中付着生物防汚剤の有効成分である本剤化合物は動物性付着生物の防汚に対して特に有効であるので、所望により植物性付着生物の防汚に有効な他の薬剤と併用することも有用であり、また、防汚効果や防汚期間を更に向上させるため、他の有機薬剤と併用しても何らさしつかえ無い。これらの目的で用いうる有機薬剤として例えば２，４，６−トリクロロフェニルマレイミド、３− (３，４−ジクロロフェニル) −１，１−ジメチルウレア（ＤＣＭＵ）、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルアミノ−Ｓ−トリアジン、テトラクロロイソフタロニトリル、４，５−ジクロロ−２−ｎ−オクチル−３（２Ｈ）イソチアゾロン、ジンクジメチルジチオカーバメイト等を例示できる。これらの有機薬剤は１種または２種以上を使用しても差し支えない。また、本発明の水中付着生物防汚剤においては例えば亜酸化銅等の銅化合物を併用しても差し支えなく、この場合の製剤化は前記のような方法で例えば前述の構成成分等を用いて塗料化すれば良く、更にはシリコン樹脂、シリコンオイル等とも併用しても差し支えない。
【００１５】
〔参考例１〕 ６−クロロインドリンの製造
窒素雰囲気下、エタノールアミン48.2g(0.78モル) 中に塩化第二銅４.2g(0.03モル) を添加し、 150℃にて２，４−ジクロロフェネチルアミン50g(0.26モル) を滴下し、同温度で2.５時間反応を行い終了とした。室温まで冷却したのち、水、トルエンを入れ、分液、トルエン層を脱水し、トルエンを留去し、残渣の赤褐色油性物を真空蒸留し、沸点89℃／２mmHgの無色液体の６−クロロインドリンを27.9g 得た（収率69.9％) 。
【００１６】
〔参考例２〕 ６−クロロ−１−アセチルインドリンの製造
６−クロロインドリン20.1g(0.13モル) 、トルエン200ml 中に室温にて無水酢酸14.7g を滴下し、90℃で２時間熟成を行い終了とした。反応終了後、トルエン及び酢酸を減圧蒸留し、残渣の無水結晶を、少量のトルエンで洗浄し、６−クロロ−１−アセチルインドリンを23.5g 得た (収率92.5％) 。
【００１７】
〔参考例３〕 ５，６−ジクロロ−インドリンの製造
６−クロロ−１−アセチルインドリン23.5g(0.12モル) 、クロロホルム50ml中に、室温にて塩化スルフリル18.5g(0.14モル) を滴下した後、４時間還流し終了とした。反応終了後クロロホルムを減圧留去し、残渣の褐色固体を冷メタノールで洗浄し、その固体を６Ｎ−塩酸・メタノール15.2ml中に入れ、４時間還流を行い終了とした。室温まで冷却し、アンモニア水でアルカリ性とし、トルエンで抽出し、トルエンを留去し、５，６−ジクロロインドリンを17g 得た (収率は75.2％) 。
【００１８】
〔参考例４〕 ５，６−ジクロロインドールの製造
５，６−ジクロロインドリン10g(0.05モル) 、キシレン350ml 中に室温にてジクロロジシアノキノン12.1g(0.05モル) を添加し、３時間還流を行い終了とした。反応終了後、10℃まで冷却し、固体を濾過し、キシレンを減圧留去し、残渣をイソプロピルエーテルで再結し、融点 148〜151℃の無色結晶５，６−ジクロロ−インドールを7.2g得た (収率72.7％) 。
【００１９】
【発明の効果】
本発明により従来のグラミン化合物を用いるものに比較して水中付着生物の付着防止効果がより改善された水中付着生物防汚剤が提供される。
【００２０】
【実施例】
以下、実施例、処方例により本発明を具体的に説明する。ただし、本発明はこれらの実施例および処方例に限定されるものではない。
【００２１】
〔実施例１〕 ５，６−ジクロロ−１−メチルグラミンの製造
５，６−ジクロロインドール1.9g(0.01モル) をジメチルホルムアミド20mlに溶解し、５℃にて60％−水素化ナトリウム0.42g(0.01モル) を添加し、同温度で30分攪拌した後、ヨウ化メチル1.5g(0.07モル) を滴下し、室温で３時間攪拌した後終了とした。反応終了後、水、トルエンを注入し、トルエン層を分液、脱水、トルエンを留去し、無色固体の５，６−ジクロロ−１−メチルインドールを粗製物として2.2g 得た。
得られた無色固体を、40％ジメチルアミン水溶液1.3ml、35％ホルマリン0.9ml、酢酸1.7mlの混合溶液中に添加し、一夜攪拌した後、アンモニア水でアルカリ性とし、析出した固体を濾過し、トルエンで再結し、無色固体の５，６−ジクロロ−１−メチルグラミンを1.6g 得た (収率61.5％) 。
【００２２】
（確認データ）
融 点：115〜116℃
¹H-NMR：7.78 (s, 1H)、7.38 (s, 1H)、6.95 (s, 1H)、3.68 (s, 3H)、
3.47 (s, 2H)、2.23 (S, 6H)
【００２３】
〔実施例２〕 室内スクリーニングにおけるタテジマフジツボキプリス幼生の付
着阻止試験
供試化合物0.0025mgまたは0.000125mgをメタノール0.１mlに溶解し、それを直径４cmの円形シャーレに均一に塗布した後、メタノールを乾燥し、更に濾過海水５mlとタテジマフジツボの付着期幼生であるキプリス幼生を10個体ずつ入れ、23℃の暗所に静置した。24時間後に取り出し、シャーレ底面に付着変態したタテジマフジツボの数を調べ、付着阻止効果を判定した。また、比較化合物として特開平６−６５００８号公報記載の類似化合物を供試した。さらに、酸化ビス（トリブチルスズ〔［bis (tributyltin) oxide 〕、以下、単に「ＴＢＴＯ」と記載することがある。〕を用いた同様の試験、および薬剤処理を行わずにタテジマフジツボの付着を観察した試験 (無処理試験) を行なった。なお、試験は３回繰り返し、その平均を求めた。結果を（表１）に示した。
【００２４】
【表１】

【００２５】
比較１の化合物にも比較的良好な付着阻止活性が認められたものの、本発明に用いる (化合物１〜５）はこれらを更に上回る活性を示した。
【００２６】
〔処方例〕
本発明の水中付着生物防汚剤を塗料として製剤する場合の処方例を下記 (表２) に示した。
【００２７】
【表２】

【００２８】
本剤化合物を含む各成分を上記（表２）の割合に配合し、実験用小型アトライターで50ミクロンまで分散して塗料として水中付着生物防汚剤を得た。[0001]
[Industrial application fields]
The present invention relates to equipment installed in the sea such as ship bottoms and fishing nets, buoys, underwater structures such as harbors and dam attachments, condenser cooling water for thermal power plants, or heat exchanger cooling water for the petrochemical industry. The present invention relates to an underwater organism antifouling agent that prevents underwater organisms such as barnacles, blue mussels and seaweed from adhering to, breeding and causing harm to intake channels.
[0002]
[Prior art]
In the past, water-fouling organism antifouling agents containing organotin compounds as active ingredients were used to prevent the growth of seawater and freshwater pests. Social problems have arisen that there is a risk of harm to the human body using fish as a medium. Therefore, the use and production of organotin compounds are subject to legal regulations, and the appearance of similar underwater biofouling agents using organic compounds instead of organotin compounds has been desired.
[0003]
Against this background, the present inventors have previously proposed an underwater biofouling antifouling agent using a gramine compound or the like as an active ingredient (JP-A-6-65008). However, a biofouling antifouling agent having an improved effect is further desired.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel compound and an aquatic organism antifouling agent having an excellent adhesion preventing effect on aquatic organisms using them.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a certain kind of gramein compound exhibits an excellent antifouling effect on aquatic organisms and have completed the present invention.
That is, the present invention provides a novel compound 5,6-dichloro-1-methylgramine represented by the following formula.
[0006]
[Chemical formula 2]

[0007]
Furthermore, the present invention relates to 5,6-dichlorogramamine, 5-chloro-2-methylgramine, 5-bromo-2-methylgramine, 1,2-dimethyl-6-bromogramamine, 5,6-dichloro-1-methyl. The present invention provides an underwater biofouling agent characterized by containing one or more selected from Grameen as an active ingredient.
In the following description, compound names are abbreviated as follows as necessary.
5,6-Dichlorogramin: (Compound 1)
5-Chloro-2-methylgramine: (Compound 2)
5-Bromo-2-methylgramine: (Compound 3)
1,2-dimethyl-6-bromogramine: (compound 4)
5,6-dichloro-1-methylgramine: (compound 5)
The present invention will be described in detail below.
[0008]
Compounds 1 to 5 (hereinafter sometimes simply referred to as “this agent compound”) used as active ingredients of the underwater biofouling agent of the present invention can be produced, for example, by the following method. It is.
5,6-Dichlorogramin can be produced by treating 5,6-dichloroindoline with dichlorodicyanoquinone or the like to give 5,6-dichloroindole, and then subjecting it to a Mannich reaction using dimethylamine and formaldehyde.
[0009]
5-Chloro-2-methylgramine is further subjected to Mannich reaction with 5-chloro-2-methylindole obtained by treating 5-chloro-2-methylindoline with dichlorodicyanoquinone or the like using dimethylamine and formaldehyde. It can be manufactured by things.
5-Bromo-2-methylgramine is a Mannich reaction of 5-bromo-2-methylindole obtained by treating 5-bromo-2-methylindoline with dichlorodicyanoquinone or the like using dimethylamine and formaldehyde. It can be manufactured by things.
[0010]
1,2-Dimethyl-6-bromogramin is obtained by N-methylation of 5-chloro-2-methylindole obtained by treating 5-chloro-2-methylindoline with dichlorodicyanoquinone or the like with methyl iodide or the like. Thereafter, it can be produced by a Mannich reaction using dimethylamine and formaldehyde.
5,6-dichloro-1-methylgramin is obtained by N-methylating 5,6-dichloroindole obtained by treating 5,6-dichloroindoline with dichlorodicyanoquinone or the like with methyl iodide or the like. It can be produced by a Mannich reaction using dimethylamine and formaldehyde. This compound is a novel compound.
[0011]
As the underwater-fouling biofouling agent of the present invention, the agent compound itself can be used as it is, but depending on the purpose and target, the agent can be used in an appropriate dosage form such as a paint, solution, emulsion, pellet, or flake. By formulating the compound, for example, equipment placed in the sea, such as ship bottoms, fishing nets, buoys, underwater structures such as dam attachments, condenser cooling water for thermal power plants, and heat exchangers for the petrochemical industry It can be used for a wide range of objects that require antifouling organisms such as cooling water intake channels. Equipment for placing the underwater biofouling agent of the present invention in the bottom of the ship and in the sea, such as fishing nets and buoys, underwater structures such as dam attachments, and water for cooling condensers of thermal power plants or petrochemical industries When used in parts that are constantly in contact with seawater, such as water intake for cooling water for heat exchangers, this compound is usually formulated into a paint, but if desired, it can be added to the intake in the form of an emulsion. May be. Further, the present compound may be formed into pellets by a method such as hot melt molding or mixed compression molding with a hydrophilic resin, a surfactant or the like, and installed in a cooling water system using seawater.
[0012]
When the agent compound is formulated as a paint, the agent compound is blended with a film-forming agent, and if necessary, a plasticizer, a color pigment, an extender pigment, and other ingredients commonly used for paint preparation, a stirrer or a three-roller A conventional disperser such as a sand mill may be used for coating. That is, for example, this agent compound, aromatics such as toluene, xylene, cumene, naphtha, alcohols such as propanol, ketones such as methyl isobutyl ketone, synthetic resins such as oil varnish and acrylic resin, synthesis Film formulation agents such as rubber and rosin, if necessary, dyes, plasticizers such as dioctyl phthalate (DOP) and chlorinated paraffin, colored pigments such as petals, or extender pigments such as barium sulfate and tackle Can be formulated into a paint. Further, the present compound can be formulated into an emulsion by blending water, for example, a solvent immiscible with water such as the aromatic hydrocarbon, and a known surfactant such as an anionic, nonionic or cationic one. Furthermore, for example, a hydrophilic resin such as polyethylene glycol that is solid at room temperature is used as a base, and the present compound and, if necessary, a plasticizer, a surfactant, and the like are blended as constituent components, and pelletized by a method such as melt molding or compression molding Or flakes. The compounding amount of this drug compound in the preparation is appropriately selected according to the conditions such as the purpose, dosage form, and method of use, and the compounding amount is not limited as long as the drug compound does not interfere with the formulation, but the drug compound For example, when it is made into a paint, solution, emulsion, etc., it is usually 1 to 40% by weight, preferably 3 to 20% by weight. When it is made into a pellet or the like, it is usually 30 to 95% by weight. Preferably, it may be blended at a ratio of 50 to 90% by weight. Other components may be those commonly used in each preparation, and the types, combinations, blending amounts, etc. are not limited to the examples in the present specification, and are appropriately in a wide range according to the desired physical properties of the preparation. Can change.
[0013]
The underwater-fouling biofouling agent of the present invention can be used by appropriately selecting a commonly used technique such as coating, impregnation, addition in water, installation in water, etc. according to the place of use, purpose and dosage form. That is, when the underwater-fouling biofouling agent of the present invention is, for example, a paint, it can be used by a method such as application to a ship bottom, a fishing net, an underwater structure, a water intake, etc. It is also possible to exemplify effective use by immersing a fishing net in the prepared underwater-fouling biofouling agent of the present invention and coating and / or impregnating it. In addition, when the target is an intake channel, a method of adding a solution or an emulsion in water, a method of adding pellets or flakes, for example, hanging or pasting, etc. are appropriately selected according to actual usage conditions The method used by the installation method of can also be illustrated. Furthermore, for example, this agent compound is incorporated in the production stage of ropes or fiber materials used for fishing nets, etc., and used in dosage forms and methods other than those exemplified above, such as imparting antifouling performance to the water or attached to the ropes or fiber materials themselves. You can also
[0014]
In addition, since the present compound, which is an active ingredient of the underwater biofouling agent of the present invention, is particularly effective for the antifouling of animal adhering organisms, other compounds effective for antifouling of plant adhering organisms as desired It is also useful to use in combination with chemicals, and in order to further improve the antifouling effect and antifouling period, it can be used in combination with other organic chemicals. Examples of organic agents that can be used for these purposes include 2,4,6-trichlorophenylmaleimide, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 2-methylthio-4-t-butylamino. Examples include -6-cyclopropylamino-S-triazine, tetrachloroisophthalonitrile, 4,5-dichloro-2-n-octyl-3 (2H) isothiazolone, zinc dimethyldithiocarbamate. These organic drugs may be used alone or in combination of two or more. In addition, in the underwater adhesion biofouling agent of the present invention, for example, a copper compound such as cuprous oxide may be used in combination, and the formulation in this case is performed using the above-described components, for example, by the above-described method. What is necessary is just to make it a paint, and also it does not interfere even if it uses silicone resin, silicone oil, etc. further.
[0015]
[Reference Example 1] Production of 6-chloroindoline In a nitrogen atmosphere, 4.2 g (0.03 mol) of cupric chloride was added to 48.2 g (0.78 mol) of ethanolamine, and 2,4-dichlorophenethylamine was added at 150 ° C. 50 g (0.26 mol) was added dropwise and the reaction was terminated at the same temperature for 2.5 hours. After cooling to room temperature, water and toluene are added, liquid separation, the toluene layer is dehydrated, toluene is distilled off, and the residual reddish brown oily substance is vacuum distilled to give a colorless liquid 6-chloroindoline having a boiling point of 89 ° C / 2 mmHg. 27.9 g (69.9% yield) was obtained.
[0016]
[Reference Example 2] Production of 6-chloro-1-acetylindoline 24.7 g (0.13 mol) of 6-chloroindoline and 14.7 g of acetic anhydride are added dropwise to 200 ml of toluene at room temperature, followed by aging at 90 ° C for 2 hours. It was. After completion of the reaction, toluene and acetic acid were distilled under reduced pressure, and the anhydrous crystals of the residue were washed with a small amount of toluene to obtain 23.5 g of 6-chloro-1-acetylindoline (yield 92.5%).
[0017]
[Reference Example 3] Production of 5,6-dichloro-indoline After adding 18.5 g (0.14 mol) of sulfuryl chloride dropwise at room temperature to 23.5 g (0.12 mol) of 6-chloro-1-acetylindoline and 50 ml of chloroform, Refluxed for 4 hours and finished. After completion of the reaction, chloroform was distilled off under reduced pressure, and the residual brown solid was washed with cold methanol. The solid was placed in 15.2 ml of 6N hydrochloric acid / methanol and refluxed for 4 hours to complete. The mixture was cooled to room temperature, made alkaline with aqueous ammonia, extracted with toluene, and toluene was distilled off to obtain 17 g of 5,6-dichloroindoline (yield: 75.2%).
[0018]
[Reference Example 4] Production of 5,6-dichloroindole Add 10 g (0.05 mol) of 5,6-dichloroindoline and 12.1 g (0.05 mol) of dichlorodicyanoquinone to 350 ml of xylene at room temperature and reflux for 3 hours. Ended. After completion of the reaction, the mixture was cooled to 10 ° C., the solid was filtered, xylene was distilled off under reduced pressure, and the residue was recrystallized with isopropyl ether to obtain 7.2 g of colorless crystal 5,6-dichloro-indole having a melting point of 148-151 ° C. (Yield 72.7%).
[0019]
【The invention's effect】
According to the present invention, there is provided an underwater-fouling biofouling agent having an improved effect of preventing the adhesion of underwater organisms compared to those using a conventional gramein compound.
[0020]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Formulation Examples. However, the present invention is not limited to these examples and formulation examples.
[0021]
[Example 1] Preparation of 5,6-dichloro-1-methylgramamine 1.9 g (0.01 mol) of 5,6-dichloroindole was dissolved in 20 ml of dimethylformamide, and 60% -0.42 g of sodium hydride at 5 ° C ( 0.01 mol) was added, and the mixture was stirred at the same temperature for 30 minutes. Then, 1.5 g (0.07 mol) of methyl iodide was added dropwise, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water and toluene were injected, the toluene layer was separated, dehydrated, and toluene was distilled off to obtain 2.2 g of colorless solid 5,6-dichloro-1-methylindole as a crude product.
The obtained colorless solid was added into a mixed solution of 40% dimethylamine aqueous solution 1.3 ml, 35% formalin 0.9 ml, and acetic acid 1.7 ml, stirred overnight, then made alkaline with aqueous ammonia, and the precipitated solid was filtered. Recrystallization from toluene gave 1.6 g of colorless solid 5,6-dichloro-1-methylgramamine (yield 61.5%).
[0022]
(Confirmation data)
Melting point: 115-116 ° C
¹ H-NMR: 7.78 (s, 1H), 7.38 (s, 1H), 6.95 (s, 1H), 3.68 (s, 3H),
3.47 (s, 2H), 2.23 (S, 6H)
[0023]
[Example 2] Adhesion inhibition test of vertebrate larvae in laboratory screening 0.0025 mg or 0.000125 mg of a test compound was dissolved in 0.1 ml of methanol, and evenly applied to a circular petri dish having a diameter of 4 cm, and then the methanol was dried. Further, 5 ml of filtered seawater and 10 cypris larvae, which are the attachment stage larvae of the vertical barnacles, were added and left in a dark place at 23 ° C. After 24 hours, it was taken out and the number of vertical barnacles attached and transformed on the bottom of the petri dish was examined to determine the adhesion prevention effect. Moreover, a similar compound described in JP-A-6-65008 was used as a comparative compound. Further, the same test using bis oxide ([bis (tributyltin) oxide], hereinafter sometimes simply referred to as “TBTO”), and the adhesion of the vertical barnacle without the chemical treatment were observed. The test (non-treatment test) was conducted, and the test was repeated three times, and the average was obtained, and the results are shown in Table 1.
[0024]
[Table 1]

[0025]
Although comparatively good adhesion-inhibiting activity was also observed in the compound of Comparative 1, the compounds (compounds 1 to 5) used in the present invention exhibited an activity exceeding these.
[0026]
[Prescription example]
A formulation example in the case of formulating the underwater biofouling agent of the present invention as a paint is shown in the following (Table 2).
[0027]
[Table 2]

[0028]
Each component containing this agent compound was blended in the proportions described above (Table 2) and dispersed to 50 microns with a small experimental attritor to obtain an underwater biofouling agent as a paint.

Claims (2)

5,6-dichloro-1-methylgramine represented by the following formula.

  1. An underwater biofouling agent containing 1,2-dimethyl-6-bromogramamine as an active ingredient.