JPH013156A - Diphenylamine derivatives and aquatic biofouling agents containing them - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel diphenylamine derivative effective as an aquatic biological antifouling agent and an aquatic biological antifouling agent containing this 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 to Solve 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 extensive research aimed at developing a novel diphenylamine derivative, which has not been described in any literature, it was unexpectedly discovered that it is highly effective against harmful aquatic organisms, particularly Fujibo, Serpura, and Murasaki mussels, leading to the completion of the present invention. Ta.

That is, the present invention is based on the formula (wherein R represents a lower alkyl group or a cyclohexyl group, X represents a hydrogen atom, a halogen atom, a nitro group, or a lower haloalkyl group, and m represents an integer from 1 to 4.

) An aquatic biological antifouling agent characterized by containing the diphenylamine derivative shown in the following formula and the diphenylamine derivative as an active ingredient.

Specific examples of the diphenylamine derivative represented by formula (1) of the present invention include the following compounds.

Compound NO, 1; 2. 4. 6-) Libromo 2',
4'-dinitro-6'-t-butyl-diphenylamine compound NO, 2;2. 6-dibromo-2'',4'-dinito0-6'-t-butyldiphenylamine compound N
O,3;4-)lifluoromethyl-2'',4'=dinitro-6'-t-butyl-diphenylamine compound N
O,4; 2', 4.4"-trinitro-6"-
t-Butyl-diphenylamine compound NO, 5; 2.2'+ 4.4'-tetranitro-6'-t-butyl-diphenylamine compound NO, 6; 2. 4. 6-) Rekuroro 2',
4'-dinitro-6'-t-butyl-diphenylamine compound NO, 7; 2, 4-dichloro-2', 4
'-dinitro-6'-t-butyl-diphenylamine compound NO, 8; 3. 4-dichloro-2', 4'-dinitro-6'-1-butyl-diphenylamine compound N
O,9,2,4,6-1-refluoro-2', 4'-
Dinitro-6″-t-butyl-diphenylamine compound NO, 10; 2.2″, 4.4′-tetranitro-6″-5ec-butyl-diphenylamine compound NO, 11; 2. 4. 6-) Rekuroro 2'
, 4'-dinitro-6'-1-butyl-diphenylamine compound NO, 12;2. 4'+ 6-Trichloro2'', 4'-dinitro-61-1-propyl-diphenylamine compound NO, 13; 2. 4. 6-Trichloro2', 4'-dinitro-61-n-propyl-diphenylamine compound NO. , 14; 2. 4. 6-Dolichloro-2', 4''-dinitro-6'-ethyl diphenylamine compound NO, 15; 2, 4.6-)lichloro-2', 4'-dini compound NO, 16; 2 .2',
4.4'-tetranitro-6'-ethyl-diphenylamine = 7- As a method for producing the diphenylamine derivative represented by the above-mentioned formula (I) of the present invention, for example, -the formula (wherein X and m are the same as above) Anilines represented by the formula (in which R has the same meaning as above and Y represents a halogen atom) are combined with a solvent and an acid bond. It can be produced by reacting in the presence of an agent at a reaction temperature of -20 to 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, hydroxide, sodium hydride, and sodium hydrogen carbonate.

The diphenylamine derivative represented by 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 diphenylamine derivative represented by formula (I) as an active ingredient is a paint containing the diphenylamine derivative.

It is used in the form of a solvent or emulsion. For example, when used as a paint, the diphenylamine derivative represented by formula (1) above can be mixed with a paint forming agent to prepare an antifouling paint, and this can be applied to the bottom of a ship, underwater structures, and walls of cooling water intake channels. can. 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 compound of the present invention is blended in an amount of 1 to 20%, preferably 2 to 10%, based on the total weight of the paint. For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the diphenylamine derivative represented by the above 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 diphenylamine derivative of the present invention as an active ingredient, it is possible to maintain a high antifouling effect for a long period of time with a low content and safely without using an organic tin compound. can.

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

Synthesis Example I C2,2',4,4'-te1-lanitrho6'-t-butyl-diphenylamine (compound NO,
Synthesis of 5)] In a 200 ml glass reaction vessel, 50 ml of toluene, 25 ml of dimethyl sulfoxide and 3.2 g of 97% sodium hydroxide powder were charged, and while stirring, 7.3 g (0.04 mol) of 2,4-dinitroaniline was added to toluene. A solution of 20 ml of dimethyl sulfoxide and 20 ml of dimethyl sulfoxide was added dropwise at room temperature. After the dropwise addition, the mixture was stirred at room temperature for 2 hours. Next, keep it at 5℃ 2. 4-dinitro-6-t
-Butyl-lylolobenzene10. 3 g (0,04
mol) to 20 ml of toluene and 20 ml of dimethyl sulfoxide.
A solution of m1 in the mixed solvent was added dropwise over a period of 45 minutes. At this time, cooling was performed so that the reaction temperature was maintained at 2 to 6°C.

After the addition was completed, the mixture was aged at room temperature for 28 hours.

After that, the reaction mixture was poured into water, 36% hydrochloric acid was added, and P H=
1, the organic matter was extracted with toluene, the acid content was washed with water, and the mixture was concentrated under reduced pressure to obtain a solid. After that, it was recrystallized from ethyl alcohol to produce a yellow powder with a melting point of 164.0-168.5.
°C 2.2”, 4.4’-tetrani 1~low 6’-t-
8.2g of butyl-diphenylamine was obtained. Yield is 50
．． It was 6%. Analysis confirmation data is shown below.

9.77 (Ill, S) Synthesis Example 2 (2,4-dichloro-2',4'-dinitro-6'-t-butyl-diphenylamine (compound NO,
Synthesis of 7)] Instead of 2,4-dinitroaniline in Synthesis Example 1, 2.
The procedure was repeated in the same manner as in Synthesis Example 1 except that 6.5 g (0.0'4 mol) of 4-dichloroaniline was used, and 2.4-dichloroaniline was obtained with yellow-orange crystals and a melting point of 1.29.5-31.0°C. 10.3 g of dichloro 2°,4'-dinitro-6'-t-butyl-diphenylamine was obtained. The yield was 67.0%.

Analysis confirmation data is shown below.

Synthesis example 3 C2,4,6-trichloro 2゛4゛ -
Synthesis of dinitro-6=t-butyl-diphenylamine (compound NO, 6)] In a 100 ml glass reaction vessel, 60% NaH2,
4.g (0.06 mol) and 25 ml of dry dimethylformamide are added, stirred and a nitrogen stream is started.

To this was added 5.9 g of 2.4.6-1-dichloroaniline (0
,03 mol) in dry dimethylformamide 15ml=1
A solution dissolved in 3--12= was added dropwise at room temperature over 15 minutes, and then aged for 1 hour.

Next, a solution of 7.8 g (0.03 mol) of 2,4-dinitro-6-t-butyl-chlorobenzene dissolved in 20 ml of dry dimethylformamide was added dropwise over 35 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, 36% hydrochloric acid was added, and P H
1, extract the organic matter with toluene, wash the acid content with water, concentrate under reduced pressure, and recrystallize with ethyl alcohol to obtain a yellow powder,
8.3 g of 2,4,6-trichloro-2'',4''-dinitro-6''-t-butyl-diphenylamine having a melting point of 177.5-178.0°C was obtained. The yield was 66%.

Analysis confirmation data is shown below.

Example 1 Nauplius larvae of Tateshima fujiburi, which had been foiled in artificial seawater, were used as test organisms by being acclimated to keylius larvae, which are sessile stage larvae, using diatoms as feed.

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

- 10 mg of the compound of the present invention was mixed with cyclohexanone and Twe
A 1 g emulsion was made with an emulsion containing 10:1 of en-80 and diluted with artificial seawater to a predetermined concentration.

1 ml of this was added to the test dish. The petri dish was left 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 LC).
. It shows. ) was sought. Further, as a comparative example, bistributyltin oxide was used and the same test was conducted below. The results are shown in Table 1.

Table 1 *Compound No. 8 in the table is the same as the above compound.

Example 2 10 mg of the compound of the present invention was added to cyclohexanone: Tuee
An emulsion having a ratio of n-80 of 10=1 is made into 1 g of emulsion, and diluted with water to give a predetermined concentration.

Take 1 ml of the above dilution water into a 10β glass aquarium and dilute it with 101 water to prepare fish toxicity test water.

On the other hand, medaka fish weighing 0.3 to 0.4 g were prepared and 10 fish were released in each test water. The number of dead individuals after 24 hours of standing in a constant temperature room at 20° C. 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 - Diphenylamine FfgR represented by formula (T)
An antifouling paint was prepared by blending the following proportions and thoroughly mixing them in a ball mill.

Compound of the present invention 5% by weight Valve Handle 10% by weight 20% by weight Zinc white 20% by weight CR-101.2% by weight Plasticizer 2% by weight Xylene 31% by weight

Claims (1)

[Claims] 1) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼・・・(I) (In the formula, R represents a lower alkyl group or a cyclohexyl group, and X represents a hydrogen atom or a halogen atom. , represents a nitro group or a lower haloalkyl group, and m represents an integer from 1 to 4.) A diphenylamine derivative represented by the following. 2) General formula▲ Numerical formula, chemical formula, table, etc.▼・・・・・・(I) (In the formula, R represents a lower alkyl group or a cyclohexyl group, and X represents a hydrogen atom, a halogen atom, a nitro group, or a lower haloalkyl group. group, m represents an integer from 1 to 4.) An aquatic biological antifouling agent characterized by containing a diphenylamine derivative represented by the following as an active ingredient.