JPS62169767A - Anilinopyridine derivative and antifouling agent containing same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is H, halogen, lower alkyl, nitro, lower haloalkyl; m is 0-4). EXAMPLE:3-(2',4'-Dinitro-6'-t-butylanilino)-2-chloropyridine. USE:An antifouling agent. PREPARATION:The reaction between a compound of formula II and another compound of formula III (Z is halogen) is conducted in a solvent such as DMF in the presence of an acid acceptor such as sodium hydroxide at -20-200 deg.C for 1-48hr to give the objective compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel anilinopyridine 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, 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 Problems) 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 aimed at developing a novel anilinopyridine derivative, the inventors discovered that a new anilinopyridine derivative, which had not been described in any literature, was surprisingly effective against harmful aquatic sessile organisms, particularly fujibo, serpura, and mussels, thereby completing the present invention. reached.

That is, the present invention is based on the general formula (wherein X is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents a 2l-or lower haloalkyl group, and m represents an integer from O to 4. ) An aquatic biological antifouling agent characterized by comprising an anilinopyridine derivative represented by the following and an active ingredient thereof.

Specific examples of the anilinopyridine derivative represented by the general formula (I) of the compound of the present invention include the following compounds.

Compound NO,1; 3- (2',4°-dinitro-6
゛-t-p compound NO,2; 2- (2°,4゛-dinitro-6゛-t-butylanilino')-5-)lifluoromethylpyridine compound NO,3i 2- (2',4'- Dinitro-6
゛-t-butylanilino)-3,5-dichloropyridine compound NO,4; 3-(2',4'-dinitro-6
"-t-butylanilino)-2,6-dichloropyridine R- Compound NO,5i 2- (2',4'-dinitro-6
"-t-butylanilino)-3-chloro-5= trifluoromethylpyridine compound NO,6; 2- (2",4"-dinitro-6
゛-t-butylanilino)-4-methylpyridine compound NO,7; 2-(2',4''-dinitro-6゛-t-butylanilino)-5-nitropyridine represented by the above general formula (I) of the present invention Examples of methods for producing aminopyridine derivatives include 2,4-dinitro derivatives represented by the general formula (wherein X and m have the same meanings as above) (wherein Z represents a halogen atom). -6-t-butyl-haloheneine in the presence of a solvent and an acid binder, generally at 120%
It can be produced by reacting at a reaction temperature of ~200°C for 1 to 48 hours. Examples of the solvent used in this case include dimethylformamide, dimethylsulfoxide, pyridine, tetrahydrofuran, toluene, etc., or a mixed solvent thereof, and preferably a mixed solvent of dimethylformamide or dimethylsulfoxide and toluene. The acid binder is a basic substance such as sodium hydroxide, potassium hydroxide, sodium hydroxide, and sodium hydrogen carbonate.

The anilinopyridine derivative represented by the general formula (1) of the present invention is useful as an aquatic biological antifouling agent. Further, the aquatic biological antifouling agent of the present invention containing the anilinopyridine derivative represented by the general formula (1) as an active ingredient is a paint containing the anilinopyridine derivative.

It is used in the form of a solvent or emulsion. For example, when used as a paint, the anilinopyridine ta'J represented by the general formula (1) is mixed with a paint forming agent to prepare an antifouling paint, and this is applied to the bottom of a ship, underwater structures, and cooling water. Can be applied to intake channel walls. Examples of the film forming agent used in this case include oil varnish, synthetic resin, and artificial rubber. Pigments and extender pigments can be added to the antifouling paint as desired. In this case, the compound of the present invention is present in an amount of 1 to 20%, preferably 2 to 10%, based on the total weight of the paint.
It is blended in the proportion of For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the anilinopyridine derivative represented by the above general formula may be added to the intake channel in the form of a solution or emulsion. However, 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 anilinopyridine R81 as an active ingredient of the present invention, high antifouling effects can be maintained for a long period of time at a low content and safely without using organic tin compounds. can do.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Synthesis example 1 (1-(2',4'-dinitro-6"-
Synthesis of t-butylanilino)-3,5-dichloropyridine (Compound No. 3) 25 ml of dimethyl sulfoxide and 6.2 g of 97% sodium hydroxide powder were charged into a 200 ml glass reaction vessel, and 2-amino-3 was prepared with stirring. , 8.2 g (0.05 mol) of 5-dichloropyridine was mixed with 15 g of dimethyl sulfoxide.
The solution dissolved in m1 was added dropwise at room temperature over a period of 15 minutes. At this time, the reaction mixture changed from colorless to yellow to greenish brown.

Next, a solution of 12.9 g (0.05 mol) of 2,4-dinitro-(,-1-butyl-chlorobenyne) dissolved in a mixed solvent of 10 ml of dimethyl sulfoxide and 10 ml of toluene was added dropwise over 45 minutes. Cooling was performed to maintain the reaction temperature at 2 to 6°C.After the dropwise addition,
It was aged for 19 hours at room temperature.

After that, the reaction mixture was poured into water and 36% hydrochloric acid was added to adjust the pH to 1. Organic substances were extracted with ethyl acetate, and the acid content was washed with water.
It was concentrated under reduced pressure to obtain a solid. Thereafter, it was recrystallized from ethyl alcohol to produce a yellow-green powder with a melting point of 167°C.
4'-dinitro-6'-t-butylanilino)-3,5
-12.1g of dichloropyridine was obtained. The yield was 63%. Analysis confirmation data is shown below.

Synthesis example 2 (2-(2',4"~dinitro6'-1
Synthesis of -butylanilino)-3-chloro-5-trifluoromethylpyridine (compound NO, 5)] Synthesis Example 1-2
-amino-3,5-dichloropyridine instead of 2-
Synthesis Example 1 except that 9.8 g (0.05 mol) of amino-3-chloro-5-trifluoromethylpyridine was used.
Proceed as above to obtain a yellow powder.

11.8 g of 2-(2'',4'-dinitro-6''-t-butylanilino)-3-chloro-5-trifluoromethylpyridine having a melting point of 162-163.5°C was obtained. Yield is 5
It was 6.5%. Analysis confirmation data is shown below.

Synthesis example 3 (3-(2"4+-dinitro-6'-t-
butylanilino)-2-chloropyridine (compound NO,
Synthesis of 1)] 20 ml of dimethylformamide is added to a 200 ml glass reaction vessel, stirred, and a nitrogen stream is started.

Add 4.0 g of 60% sodium hydroxide to it.

Next, 6.4 g of 3-amino-2-chloropyridine (0,
A solution of 0.05 mol) dissolved in 15 ml of dimethylformamide was added dropwise at room temperature over 15 minutes, and then aged for 1 hour.

Next, a solution of 12.9 g (0.05 mol) of 2,4-dinitro-6-t-butyl-chlorobenzene dissolved in 201 dimethylformamide was added dropwise over 60 minutes. At this time, cooling was continued so that the reaction temperature was maintained at -10 to -20°C. At this time, the reaction solution turned reddish brown. After the dropwise addition was completed, aging was carried out at room temperature for 5 hours.

After that, the reaction mixture was poured into water and 36% hydrochloric acid was added to adjust the pH to 1.
The organic matter was extracted with toluene, the acid content was washed with water, and then recrystallized with ethyl alcohol to produce a yellowish brown powder with a melting point of 160-1
7.2 g of 1(2',4'-dinitro-6'-t-butylanilino)-2-chloropyridine at 63°C was obtained. The yield was 41%. Analysis confirmation data is shown below.

Synthesis example 4 (2-(2',4'-dinitro-6゛-t
Synthesis of -butylanilino)-5-trifluoromethylpyridine (Compound No. 2) Instead of 3-amino-2-chloropyridine in Synthesis Example 3, 2-amino-5-trifluoromethylpyridine8.
Synthesis example 3 except that 1 g (0.05 mol) was used.
The same procedure as above was carried out to obtain a yellow powder, 2-(
2',4''-dinitro-6'-t-butylanilino)-
5-) 4.3g of trifluoromethylpyridine was obtained. The yield was 22.6%. Analysis confirmation data is shown below.

Example 1 Nauplius larvae of the Nauplius, which were paralyzed in artificial seawater, were used as test organisms by being acclimated to the attachment stage larvae, Nauplius larvae, using silicon rings as feed.

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.
A 10 g emulsion was made with an emulsion having a ratio of n-80 to 1081, and diluted with artificial seawater to a predetermined concentration.

This No. 11 was added to the above-mentioned test Petri dish. The petri dish was left in a constant temperature room at 20°C, and the number of dead individuals was counted after 24 hours.
This test was repeated three times to determine the half-lethal concentration (hereinafter referred to as LC2°). Comparison = 13 - A similar test was conducted using bistributyltin oxide as an example. The results are shown in Table 1.

Table 1 * Compound No. in the table has the same meaning as the above compound.

Example 2 50 mg of the compound of the present invention was added to cyclohexanone: Twee
A 10 g emulsion was made with an emulsion having a ratio of n--80 of 10:1, and diluted with water to a predetermined concentration.

Take 1 ml of the above dilution water into a 1 (liter) glass aquarium and dilute with 101 water to use as fish toxicity test water.

On the other hand, medaka fish weighing 0.3 to 0.4 g were prepared and 10 of each were released into the test water. Leave it in a constant temperature room at 20℃ 2
The number of dead individuals after 4 hours was counted, and this test was repeated three times to determine the half-lethal concentration (TLm). Furthermore, a similar test was conducted using bistributyltin oxide as a comparative example.

The results are shown in Table 2.

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

Compound of the present invention 5% by weight Valve Handle lO weight% Tar 20% by weight Zinc white 20% by weight CR-1012 weight% Plasticizer 2% by weight

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼…………(I) (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents a nitro group or a lower haloalkyl group, and m represents an integer from 0 to 4. ) Anilinopyridine derivative represented by 2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…………(I) (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents a nitro group or a lower haloalkyl group, and m represents an integer from 0 to 4. ) An aquatic biological antifouling agent characterized by containing an anilinopyridine derivative represented by the following as an active ingredient.