JPS6056136B2 - 1-(Substituted thio-carbonyl)indoline compound and aquatic organism repellent comprising this compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 1-(substituted thio-carbonyl)indoline compound and an aquatic organism repellent comprising this compound.

At all times, such as the bottom of ships, fishing nets, equipment placed in seawater such as fishing nets, underwater structures such as auxiliary equipment for toms, water intake channels for cooling condensers in thermal power plants, water for cooling heat exchangers in various industries, etc. On parts that come into contact with water, shellfish such as barnacles, snails, mussels, hydrobugs, serpura, bryozoans, sea squirts, sea lettuce, blue seaweed, and seaweed, as well as algae, adhere to and propagate on parts that come into contact with water. ,
This not only causes an increase in fuel consumption, but also economic losses due to cleaning costs for cleaning the bottom of the ship or suspension of ship operations during this cleaning period. In addition, the amount of water intake in intake channels for condensers, vessels, heat exchangers, etc. will decrease, and cooling efficiency will not only decrease, but also biomass that have fallen off the channel walls and been washed away. This is a cause of large losses, such as deterioration of the performance of equipment.

Therefore, in order to prevent problems caused by attached breeding of seawater and freshwater harmful organisms, heavy metal compounds such as copper oxide and mercury oxide, organic tin compounds such as tributyltin oxide, and organic Antifouling paints containing chlorine, organic sulfur compounds, arsenic compounds such as phenarsazine chloride, etc. are used, and in cooling water intake channels, chlorine or formalin, etc. are added directly to the waterways. was being carried out.

However, although these conventional aquatic organism repellents are effective, they have poor storage stability, their effectiveness deteriorates depending on the usage environment, their effectiveness against shellfish and algae is selective, or they corrode the coating materials. , and others, each of which has its advantages and disadvantages, and is not necessarily satisfactory in practice.

In order to solve this problem, the present inventors synthesized various compounds, investigated their repellent effects on harmful aquatic organisms, and conducted extensive research. As a result, a new 1-(substituted thio-carbonyl)indoline compound represented by the following formula was developed. The present invention was completed based on the discovery that it is effective in repelling harmful aquatic organisms.
The novel 1-(substituted thio-carbonyl)indoline compound of the present invention has the general formula (wherein A is an allyl group, a provinyl group,
Benji! represents a substituted benzyl group having one or more nitrogen atoms or lower alkyl groups, or a naphthylmethyl group.

).

Examples of the novel 1-(substituted thio-carbonyl)i5-indoline compounds of the present invention include the following.

(1) 1-(allylthio-carbonyl)indoline (2
) 1-(2-provinylthiocarbonyl)indoline (3) 1-(benzylthio-carbonyl)indoline (
4) 1-(4-chlorobenzylthiocarbonyl)indoline (5) 1-(2-chlorobenzylthiocarbonyl)indoline (6) 1-(4-bromobenzylthiocarbonyl)indoline (7) 1-( 3-fluorobenzylthiocarbonyl)indoline (8) 1-(4-ethylbenzylthiocarbonyl)indoline (9) 1-
(4-n-butylbenzylthiocarbonyl)indoline [phase] 1-(2,4-dichlorobenzylthiocarbonyl)indoline AIl-(2,4-dimethylbenzylthiocarbonyl)indoline A2) 1-(2, 4,6
-trichlorobenzylthiocarbonyl)indoline (
13) 1-(α-Naphthylmethylthiocarbonyl)indoline The novel 1-(substituted thio-carbonyl)indoline compound of the present invention can be obtained by reacting indoline, triethylamine and carbonyl sulfide in an inert solvent, for example, as shown in the reaction formula below. The general formula (
In the formula, X represents a halogen atom, and A has the same meaning as above.

) can be synthesized by reacting the hydroxylated hydrocarbons shown in ().

(In the formula, X and A represent the same meanings as above.

) In order to use the novel compound of the present invention as an aquatic organism repellent, the novel compound of the present invention is blended with various auxiliary agents, such as film forming agents, etc., and prepared in the form of paint, resin solution, emulsion, wettable powder, etc. Prepare and use.

For example, the aquatic organism repellent of the present invention can be used on ships, cooling water intake channels,
When used for underwater structures, etc., the novel compound of the present invention is mixed with a film-forming agent, prepared in the form of a paint, and used by coating. At this time, as the coating film forming agent, for example, oil varnish, rosin, synthetic resin, artificial rubber, etc. are used.
If desired, extender pigments, iron oxide pigments, or suitable coloring pigments can be added to the paint. When preparing a paint, the novel compound of the present invention is added to the paint in an amount of 5 to 80%.
%, but preferably 5 to 30%. For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the aquatic organism repellent of the present invention may be added into the intake channel in the form of a resin 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. In addition, when the aquatic organism repellent of the present invention is used in fishing nets, the novel compound of the present invention is dissolved in an organic solvent together with a resin to prepare a resin solution, the fishing net is impregnated with this resin solution, and then dried. and use it. At this time, as the resin, for example, vinyl chloride resin, phenol resin, alkyd resin, chlorinated rubber, etc. are used.
In addition, examples of organic solvents include benzene, toluene,
Xylene, chloroform, etc. are used, but if the resin is difficult to dissolve, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide may be mixed in an amount of 2 to 2% by weight. Furthermore, if the resin is more difficult to dissolve, it can be used in a suspended state. When preparing a resin solution, the novel compound of the present invention is preferably blended in the resin solution at a ratio of 1 to 30%, preferably 5 to 10%, and the resin is blended in a ratio of 3 to 20%, preferably 5 to 10%. Next, examples of the present invention will be shown.

Example 1 (Synthesis example) Indoline 15.5f1 triethylamine 13.0f11 and 300ml of toluene were placed in a 1e four-necked reaction flask equipped with a thermometer, stirrer, cooling tube, and gas inlet, and ice-cooled and stirred. of carbonyl sulfide.

After completion of the reaction, the precipitated colorless crystals were filtered with suction and washed with petroleum ether to obtain 30.0 y of 1-(triethylammoniumthio-carbonyl)indoline.

Next, 16.8 f of 1-(ethylammoniumthio-carbonyl)indoline was added to a 250 ml four-necked reaction flask equipped with a thermometer, stirrer, dropping load and condenser.
and suspended in acetone 150TrL1. 7.6 f of benzyl chloride was added dropwise to this via a dropwise load at room temperature. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for 5 hours while stirring. After the reaction was completed, the reaction solution was concentrated to dryness, and the obtained solid was washed with water and dried to obtain colorless foliar crystals. This was recrystallized from benzene to obtain Compound (3) 1-(benzylthio-carbonyl)indo"phosphorus 14.0f. The compound was identified by gas chromatography, infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc. Structural formula Appearance Colorless foliate crystals Yield 87.0% Melting point 74.0-76.5°C Example 2 (Synthesis example) Propargyl chloride as halogenated hydrocarbon 4.5
Compound (2) was prepared in the same manner as in Example 1 except that f was used.
1-(2-propenylthiocarbonyl)indoline 1
Obtained 2.0y.

Structural formula Appearance Light brown needle crystals Yield 92.1% Melting point 80.5-81.5°C Example 3 (Synthesis example) Same as Example 1 except that allyl chloride 4.6f was used as the halogenated hydrocarbon. Compound (1) 1-
(Allylthio-carbonyl)indoline 12.1' was obtained.

Structural formula Appearance Reddish brown liquid Yield 92.2% Example 4 (Synthesis example) Compound (4) 1 was prepared in the same manner as in Example 1 except that 9.7y of 4-chlorobenzyl chloride was used as the halogenated hydrocarbon. -(4-chlorobenzylthiocarbonyl)indoline 1&0y was obtained.

Structural formula Appearance Pale brown disk-like crystals Yield 98.8% Melting point 139.0-142.0C 1 Example 5 (Synthesis example) Implementation except that 2-chlorobenzyl chloride 9.7f was used as the halogenated hydrocarbon Compound (5) 1-(2-chlorobenzylthiocarbonyl)
Indoline 17.0f was obtained.

Structural formula Appearance Colorless disk-like crystals Yield 94.2% Melting point 12 & 0 to 131.0°C Example 6 (Synthesis example) Same as Example 1 except that α-chloromethylnaphthalene 10.0f1 was used as the halogenated hydrocarbon. Compound (13) 1-(α-naphthylmethylthiocarbonyl)indoline 14.5y was obtained.

Structural formula Appearance Colorless solid Yield 76.3% Melting point 111.5-113. (substitute) Example 7 (Synthesis example) Compound (11) 1 (2,4-dimethylbenzyl 15.5f of indoline (thiocarbonyl) was obtained.

Structural formula Appearance Colorless disk-like crystals Yield 87.0% Melting point 126.0-127.00C Example 8 (Synthesis example) Same as Example 1 except that 4-ethylbenzyl chloride 9.3f was used as the halogenated hydrocarbon. In the same manner, compound (8) 1-(4-ethylbenzylthiocarbonyl)
Indoline 13.3f was obtained.

Structural formula Appearance Colorless scaly crystals Yield 74.5% Melting point 92.0-9.00C Next, a seawater immersion test for the aquatic organism repellent effect using the novel compound of the present invention will be described.

Example 9 (Seawater immersion test) The novel compounds of the present invention (compounds 1 to 13) were mixed in the following proportions and thoroughly ground and mixed in a ball mill to prepare an antifouling paint.

(% indicates weight percentage.) This antifouling paint was pretreated once with wash primer and twice with antirust paint (no chemical additives), and then applied with a brush twice on a steel plate (300 x 100 x 1 m). A test plate was prepared. This test plate was fitted into a wooden frame and suspended from an immersion raft in seawater and maintained at a depth of 1.5 m.

A test plate that had been immersed in seawater was pulled up every month, and the degree of adhesion of living organisms such as shellfish and algae on the test plate was expressed as a percentage of the total area of adhesion. The results are shown in the table below. jNext, we will discuss an example of the method applied to fishing nets.

Example 10 (Fishing net test) The novel compounds of the present invention (compounds 1 to 13) were blended in the following proportions and sufficiently stirred to prepare a resin liquid.

) The resin liquid prepared in this manner was stirred well, and polyamide fibers (manufactured by Toray Industries, Inc., trade name: Alamin) were added to the mixture.
A fishing net (11-node mesh) was soaked, thoroughly impregnated with resin liquid, air-dried for 1 m, and antifouling treated to make 65 x 65 C7! A test piece was cut to a size of 1, stretched on a 60×ωo iron frame, suspended in seawater from an immersion raft, and maintained at a depth of 1.5n1. The fishing nets that had been immersed in seawater in this way were pulled out after one month and the state of harmful algae adhesion was observed and measured.

The results are shown in the table below. These results are indicated using the following evaluation symbols.

1 No adhesion at all ± Scattered attachment ＋ A small amount of adhesion throughout the net 廿 A large amount of adhesion throughout the net.

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, A is an allyl group, a propynyl group, a benzyl group, a substituted benzyl group having one or more halogen atoms or lower alkyl groups, or naphthyl 1-(substituted thio-carbonyl)indoline compound represented by (represents a methyl group). 2 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A represents an allyl group, a propynyl group, a benzyl group, a substituted benzyl group having one or more halogen atoms or lower alkyl groups, or a naphthylmethyl group.) An aquatic organism repellent characterized by containing a 1-(substituted thio-carbonyl)indoline compound as an active ingredient.