JPH01268660A - Naphthoquinone derivative and aquatic antifouling agent containing said derivative - Google Patents

Abstract

NEW MATERIAL:The naphthoquinone derivative of formula I (R<1> and R<2> are H or alkyl; X is halogen; R<1> and R<2> are not H at the same time). EXAMPLE:2,3-Dimethyl-7-chloro-5,8,4a,8a-tetrahydro-1,4-naphthoquinone. USE:Useful as an antifouling agent for aquatic life. An antifouling paint prepared by compounding said compound to a paint-forming agent is applied to ship bottom, underwater construction, etc. High antifouling effect can be safely maintained for a long period at a low concentration of the compound without using organic tin compounds. PREPARATION:The compound of formula I can be produced by reacting a p-benzoquinone derivative of formula II with a 2-halobutadiene of formula III (X is halogen) in a solvent or in the absence of solvent preferably at a temperature between room temperature and 150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel naphthoquinone derivative effective as an aquatic biological antifouling agent and an aquatic biological antifouling agent containing the same as an active ingredient.

(Prior art) Equipment placed under the sea such as the bottom of a ship, fishing nets, and buoys, dam accessory equipment, underwater structures such as bridge piers, and thermal power plants 2
Parts that are in constant contact with water, such as the cooling water intake channels of heat exchangers in the petrochemical industry, are exposed to fujibo, oysters, mussels, hydrobugs, serpura, bryozoans, sea squirts, bulrushes, and sea lettuce.

Shellfish and algae, such as blue laver and seaweed, propagate, and these attached organisms cause undesirable conditions such as increased fluid resistance, decreased thermal conductivity, etc., and reduced equipment functionality.

Conventionally, various antifouling agents have been used to prevent the adhesion and propagation of such seawater and freshwater harmful organisms. Cuprous oxide, organic tin compounds, and the like have been known as active ingredients of such antifouling agents (see Japanese Patent Publication No. 34-15526) and are still widely used. These active ingredients are contained in the paint in an amount of 10 to 50% and are eluted in seawater to prevent attachment of harmful organisms.

(Problems to be solved by the invention) Recently, however, heavy metals and harmful elements have caused social problems such as contamination of environments such as rivers and seawater, and even harm to the human body through fish. The use of organic tin compounds and the like in antifouling agents is now being advised.

(Means for solving the problem) In view of the current situation, the present inventors have developed a non-metallic organic compound other than organotin compounds that is safe and has a high antifouling effect at a low dose. As a result of intensive research to develop a new naphthoquinone derivative, which has not been described in any literature, surprisingly, it is an aquatic animal substance.

The present invention was completed based on the discovery that it has an excellent repellent effect against plant matter.

That is, the present invention is based on the general formula (where R' and R2 each represent a hydrogen atom or an alkyl group, and X represents a halogen atom).

However, this excludes the case where both R1 and R2 are hydrogen atoms. ) This is an aquatic biological antifouling agent characterized by containing the naphthoquinone derivative shown in the following formula and the naphthoquinone derivative as an active ingredient.

Specific examples of the naphthoquinone derivative represented by the general formula (1) of the present invention include the following compounds. In addition, compound No. is referred to in the following description.

Compound NO,1i 2-methyl-6-chloro-milk 8.4
a.

8a-Tetrahydro-1,4-naphthoquinone compound NO
,2i 2-methyl-7-chloro-5+8.4a.

8a-Tetrahydro-1,4-naphthoquinone compound NO
,3;2,3-dimethyl-6-chloro-5°8.4a,
8a-Tetrahydro-1,4-naphthoquinone compound N
o, 4; 2-ethyl-6-chloro-5+8.4a
.

8a-Tetrahydro-1,4-naphthoquinone compound No.
, 5; 2-ethyl-7-chloro-5,8,4a.

8a-tetrahydro-184-naphthoquinone compound No.
, 6; 2-methyl-7-bromo-5,8,4a.

8a-Tetrahydro-1,4-naphthoquinone compound No.
, 7 i 2-octyl-7-chloro-5,8゜4a
, 8a-tetrahydro-1,4-naphthoquinone compound N
o, 8; 2-methyl-3-butyl-6-chloro-
5+ 8+ 4a, 3a-tetrahydro-1,4-naphthoquinone, etc. and their tautomers 1,4-
Dihydroxy-5,8-dihydronaphthalene derivatives are mentioned.

Naphthoquinone 8W represented by the general formula (1) of the present invention
As a method for producing the J'L body, for example, general 2 (in the formula R
1 and R2 have the same meanings as above, p-benzoquinone Li 4 body represented by) and general II z C=
It can be synthesized by reacting with 2-halobutadiene represented by CCH=CHz (in the formula, X represents a halogen atom) in a solvent or without a solvent according to a conventional method. Solvents used at this time include benzene, toluene,
Aromatic solvents such as xylene and chlorobenzene, ether, and tetrahydrofuran.

Examples include ether solvents such as dioxane, and mixed solvents thereof. The reaction proceeds smoothly at a reaction temperature ranging from room temperature to 150°C.

The naphthoquinone derivative represented by the general formula (1) of the present invention is useful as an aquatic biological antifouling agent.

In addition, the aquatic biological antifouling agent of the present invention containing the naphthoquinone derivative represented by the general formula (1) as an active ingredient can be prepared by adding one or more mixtures of naphthoquinone derivatives and their tautomers to paints, solvents, It is prepared and used in the form of an emulsion. For example, when used as a paint, the above general formula (1)
An antifouling paint can be prepared by blending the naphthoquinone derivative represented by the formula with a paint forming agent, and this can be applied to the bottom of a ship, an underwater structure, and the walls of a cooling water intake channel. Examples of the coating film forming agent used in this case include oil varnish, synthetic resin 2-artificial rubber, and the like. Pigments and extender pigments can be added to the antifouling paint as desired.

In this case, the amount of the compound of the present invention is 1 to 20% based on the total weight of the paint.
%, preferably 2 to 10%. For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the naphthoquinone derivative represented by the above general formula may be added into the intake channel in the form of a solution or emulsion. but,
In order to maintain the antifouling effect for a long period of time, it is preferable to apply it in the form of a paint.

(Effects of the Invention) According to the aquatic biological antifouling agent containing the naphthoquinone derivative L form as an active ingredient of the present invention, a high antifouling effect can be maintained for a long period of time with a low content and safely without using an organic tin compound. be able to.

(Example) EXAMPLES The present invention will be explained in further detail with reference to Examples.

Synthesis Example 1 2-methyl-p-benzoquinone 2.0g (16.4mm
o+) and 4 ml of 2-chlorobutadiene (43,3 mmo
1) was refluxed in 12 ml of benzene for 9 hours. After cooling,
By distilling off the solvent, 2-methyl-6-chloro-5
,8,4a,8a-tetrahydro-1,4-naphthoquinone (compound No. 1) and 2-methyl-7-chloro-5
+8+4a, 3.45 g as a mixture of 8a-tetrahydro-1,4-naphthoquinone (compound No. 2) (
A powder solid crystal was obtained with a quantitative yield.

By recrystallizing this with ethanol, the melting point was 75.
A white powder crystal of ~78°C was obtained.

Analysis confirmation data is shown below.

I R (KBr); 1690.1670.1620.
1420.1270.1195 cm-'N M R (
CDCl2) iδ=2.00, 2.03 (2S, 3+
1).

2.2-2.85 (m, 4) 1).

2.9-3.6 (m, 211), 5.3-5.6 (lI
l, LH) 6.55 (s, III) MS; m/e 212 (M ”+2), 210 (M”
) Synthesis Example 2 2.3-dimethyl-p-benzoquinone 0.64g (5
, 3 mmol) and 2-chlorobutadiene 1 ml (10,
8 mmol) was refluxed in 3 ml of benzene for 5 hours.

After cooling, the solvent was distilled off to give 2,3-dimethyl-7-chloro-
1.12 g (quantitative yield) of 5,8,4a,8a-tetrahydro-1°4-naphthoquinone (compound NO', 3) as a solid was obtained. This was recrystallized from ethanol, with a melting point of 1
White needle-like crystals of 10-111'C were obtained.

Analysis confirmation data is shown below.

I R (KBr); 1660.1610.1375.
1305.1240.1080.790°730cm
-' N M R (CDC13); δ=2.0O (S, 6H
), 2.3-2.8(m, 4tlL3.0-3.5(
m, 211), 5.60-5.85 (m, III)
M S ; m/e 224 (M”) Test Examples 1-2 (
Test for inhibiting the growth of barnacles) Nauplius larvae of Nauplius larvae, which had grown into larvae in artificial seawater, were habituated to keylius larvae, which are attachment stage larvae, using silicon rings as feed, and used as test organisms.

19ml of artificial seawater containing 10 of these larvae was 5cm in diameter.
Transfer to a petri dish.

50 mg of the compound of the present invention was mixed with cyclohexanone and Twee.
An emulsion containing n-80 and 10=1 is used to make 1 g of emulsion, and diluted with artificial seawater to a predetermined concentration.

1 ml of this was added to the test dish. The petri dish was placed in a constant temperature room at 20°C, the number of dead individuals was counted after 24 hours, and this test was repeated three times to determine the half-lethal concentration (hereinafter referred to as LCso).
It shows. ) was sought. The results are shown in Table 1.

Test Examples 3 to 4 (Algae Growth Inhibition Test) Using the algae collected from the sea as the test algae, 5 g of it was atomized in a mortar, diluted with 11 ml of seawater, and filtered using gauze. When filtered seawater was observed under a microscope, large numbers of Aonori spores were seen moving. 19 ml of seawater containing the spores was transferred to a Petri dish with a diameter of 5 cm and used as a sample.

50 mg of the compound of the present invention was made into a 1 g emulsion with an emulsion containing cyclohexanone and Tween-80 (trade name, manufactured by Atlas Powder Co., Ltd.) in a ratio of 1O:1, diluted with seawater to a predetermined concentration, and 1 ml of the emulsion was prepared as described above. was added to a petri dish containing seawater containing nori spores. The petri dish was left standing in a constant temperature room at 20°C, and after 1 hour, a drop of its contents was transferred to a slide glass, and the presence or absence of spore movement was examined under a microscope.

The test was repeated three times to determine the growth-inhibiting concentration of the Japanese blue laver. The results are shown in Table 2.

Table 2 Formulation Example 1 Using the naphthoquinone derivative represented by the above general formula (I), an antifouling paint was prepared by blending the naphthoquinone derivative in the following proportions and thoroughly mixing in a ball mill.

Compound of the present invention 5% by weight Valve handle 10% by weight Tarri 20% by weight Zinc white
20% by weight CR-1012% by weight Plasticizer 2x% Xylene 31% by weight *CR-10, chlorinated rubber resin (manufactured by Asahi Denka ■) Formulation Example 2 (
Preparation of solution) A solution was prepared by blending the naphthoquinone derivative represented by the general formula (1) in the following proportions and sufficiently grinding and mixing in a bot mill.

Compound of general formula (1) 10% by weight Rosin ww 13% by weight Toyoba Flux A40 1
11% xylene 76% by weight *40 to Toyoparafukusu; Chlorinated paraffin, Toyo Soda a
1 company patent applicant: Sumo Central Research Institute

Claims (1)

[Claims] 1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, R^1 and R^2 each represent a hydrogen atom or an alkyl group, and X represents a halogen atom. However, this excludes the case where R^1 and R^2 are both hydrogen atoms.) The naphthoquinone derivatives shown. 2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (In the formula, R^1 and R^2 each represent a hydrogen atom or an alkyl group, and X represents a halogen atom. However, this excludes the case where R^1 and R^2 are both hydrogen atoms.) An aquatic biological antifouling agent characterized by containing the following naphthoquinone derivative as an active ingredient.