JPS6029393B2 - 3-amino-1,3-thiazolidine-2,4-dione compound, method for producing the same, and aquatic organism repellent comprising the compound - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel 3-amino-1,3-thiazolidine-2.
The present invention relates to a 4-dione compound, a method for producing the same, and an aquatic organism repellent comprising the compound. Currently, vessels' bottoms, fishing nets, wave power generation buoys, industrial cooling water intakes and passageways, underwater structures, and other vessels and equipment that are submerged in water for long periods of time are contaminated with barnacles, oysters, mussels, and hydromass. , selbula, bryozoan,
Shellfish, molluscs, and algae, such as sea squirts, sea breams, sea lettuce, blue seaweed, and seaweed, propagate, causing many damage and losses. For example, in ships, it not only causes a decrease in sailing speed and waste of fuel, but also causes economic losses such as losses due to suspension of ship operations and cleaning costs due to cleaning the bottom of the ship, and inconvenient handling of underwater structures. In addition, the amount of water taken in the water intake channels for condenser cooling and heat exchanger cooling not only decreases and the cooling efficiency decreases, but also the biomass that has fallen off the channel walls and is washed away causes regeneration. Many failures and losses have occurred, including deterioration in the performance of water appliances and heat exchangers, resulting in large economic losses. In addition, in fixed fishing nets used in fish and shellfish aquaculture for the purpose of securing marine resources as an inlet, the durability of the nets may be impaired or the meshes may become blocked due to the attachment of the above-mentioned harmful organisms. Insufficient movement of seawater within the net results in fish dying due to lack of oxygen, and also promotes the proliferation of bacteria, causing damage to fish due to Nocardia disease, Benedeniasis, etc. In order to solve these problems, the present inventors synthesized various compounds, investigated their aquatic organism repellent effects, and as a result of extensive research, we discovered a novel 3-amino-1,3-thiazolidine-2 represented by the following formula. - We have discovered that 4-dione compounds are useful for preventing the attachment of aquatic pests, and have completed the present invention. Novel 3-amino-1,3-thiazolidine-2 of this invention
・The 4-dione compound has the general formula (R in the formula is a hydrogen atom,
It represents a lower alkyl group, a halogen-substituted phenyl group or a phenylthio group, and R2 represents a hydrogen atom or a lower alkyl group. ). Examples of the novel 3-amino-1,3-thiazolidine-2,4-dione compounds of the present invention include the following. Note that the compound numbers are referred to in the Examples below. Compound {1'3-amino-1,3-thiazolidine-2,4
-dione compound [2] 3-amino-5-methyl-1.3
-thiazolidine-2,4-dione compound {3' 3-amino-5-(4-chlorophenyl)-1,3-thiazolidine-2,4-dione compound side 3-amino-5-phenylthio-1,3-thiazolidine-2,4-dione compound { 5} 3-amino-5,5-dimethyl-1,3-thiazolidine-2,4-dione compound {61 3-amino-5-ethyl-1,3-thiazolidine-2,4-dione compound '7) 3-amino-5,5-jethyl-1,3
-thiazolidine-2,4-dione The novel compound according to the present invention comprises a hydrazinethiol carbamate alkali metal salt represented by the following general formula [1] (in which M represents an alkali metal atom) and a general formula [D] (formula R and R2 are the same as above, R3 represents a lower alkyl group,
× indicates a halogen atom. ) The reaction formula is as follows. (R, , R2, R3, M and X in the formula are the same as the groups and atoms described above.) The alkali metal hydrazinethiol carbamate used as a raw material for synthesizing the novel compound according to the present invention Salt [1] can be obtained by reacting hydrazine hydrate with carbonyl sulfide in alcohol in the presence of an alcoholate such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, etc., as shown in the reaction formula below. (In the formula, R represents a methyl group or an ethyl group, and M represents an alkali metal atom.) Sodium hydrazinethiolcarbamate, potassium hydrazinethiolcarbamate, etc. are used. The other raw material, Q-halocarboxylic acid ester, has the general formula

The group represented by R in [0] is a hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 0-chloro (or monopromo) phenyl group, m-chloro ( or -bromo)phenyl group, P-chloro(or -bromo)phenyl group, or phenylthio group, and the group represented by R2 is a hydrogen atom or a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group. group or iso-butyl group, and the group represented by R3 is an alkyl group having C to C4 carbon atoms such as a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, and further represented by A compound in which the atom contained in the compound is a chloro atom, a bromine atom, or a fluorine atom, such as chloroacetic acid, bromoacetic acid, Q-chloropropionic acid, Q-bromopropionic acid, Q-chloro-n-butyric acid, Q-from-n
-butyric acid-, Q-chloro-lso-butyric acid-, Q-from-
lso-butyric acid-, 2-chloro-2-methyl-butyric acid-, 2
-fromu-2-methyl-butyric acid-, 2-chloro-2-ethyl-butyric acid-, 2-fromu-2-ethyl-butyric acid-, 2-chloro-2-P-(or 0-)chlorphenyl-acetic acid-
, 2-fromu 21P-(or 0-1)-chlorophenyl-acetic acid-, 2-chloro-2-thiophenyl-acetic acid-,
2-bromo-2-thiophenyl-acetic acid, methyl, ethyl, n-ph. Lopil, lsouf. Lopyl, n-butyl or jso-butyl esters are used. This hydrazinethiol carbamate alkali metal salt [1] and Q-halocarponic acid ester

The reaction with [0] proceeds without a solvent, but in a solvent at 5°C to 70qo, preferably 1
The reaction is carried out at a temperature range of 5q0 to 40qo for 1 hour to 8 hours, preferably 3 hours to 5 hours. Hydrazine thiol carbamate alkali metal salt [1] and Q-halocarboxylic acid ester [B] may be used in equimolar amounts, but preferably Q-halocarboxylic acid ester

It is better to use a slight excess of [0]. In addition, suitable solvents are particularly preferred as the solvent used, and examples of such polar solvents include water, nitriles such as acetonitrile, propionitrile, and benzonitrile, methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Alcohols such as, methyl formate, methyl acetate,
Examples include esters such as ethyl acetate and ethyl propionate, and aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethylene glycol-diethyl eneal, and tetramethylene glycol-dimethyl eneal. be able to. The novel compound of this invention can be used in paints,
It can be prepared in the form of a solution, emulsion, etc. and used as an aquatic organism repellent. For example, an antifouling paint is prepared by blending one or more of the novel compounds of this invention with a film forming agent, and this is applied to the bottom of a ship,
By applying it to the walls of underwater structures and cooling water intake channels, it is possible to prevent the adhesion and propagation of aquatic organisms. 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 general formula [1] is blended in an amount of 5 to 80%, preferably 10 to 50%, based on the weight of the coating film forming agent. For the purpose of preventing the adhesion and propagation of water exudates in the cooling water intake channel, the compound of general formula [1] 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 time, it is desirable to apply it in the form of a paint. In addition, when applying the novel compound of the present invention as an aquatic organism repellent for fishing nets, the novel compound of the present invention is dissolved in an organic solvent together with a resin to form a resin solution, and the fishing net is impregnated with this resin solution and dried. . When preparing this resin solution, the compound of general formula [1] is used at a concentration of 5 to 5% by weight, preferably 10 to 3% by weight, and the resin is used at a concentration of 5 to 15% by weight, preferably 7 to 1a% by weight. Dissolved in organic solvent. Examples of the resin used for preparing the resin solution include vinyl chloride resin, phenol resin, alkyd resin, and chlorinated rubber. In addition, as an organic solvent, benzene, toluene, xylene, chloroform, etc. are used, but if the resin is too much to dissolve, dimethylformamide, dimethylacetamide or dimethyl sulfoxide may be mixed in an amount of 5 to 1%. be able to. There are no particular restrictions on the material of fishing nets that can be treated with the aquatic organism repellent of the present invention. For example, natural fibers such as cotton, linen, silk, wool, polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride,
It can be applied to fishing nets made of synthetic fibers such as polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile.
Next, examples of the present invention will be shown. Example 1 Synthesis of Compound '1' A 200-sized upper four-necked flask equipped with a thermometer, a condenser, and a frame breaker was charged with 10.9 mols (0.1 mol) of methyl monochloroacetate and 1 mol of methanol, and then To this solution, 11.4 mol (0.1 mol) of sodium hydrazinethiol carbamate was added at room temperature, and the mixture was reacted for 3 hours under a 20 mol oven. As the reaction progressed, the reaction solution initially generated some heat and gradually became a transparent liquid, and then became cloudy due to the precipitation of common salt.
After the completion of the reaction, the precipitated salt was separated in a furnace, and the resulting furnace liquid was concentrated to remove methanol, and then distilled under reduced pressure to obtain 3-amino-1,3-thiazolidine-2, a colorless transparent liquid represented by the following structural formula. 12.3 ta of 4-dione was obtained. Structural formula yield 93.2% Physical properties b. p143~145℃/0.06 side Hg elemental analysis C (%) Day (%) N (%) S (%) Theoretical value 2
7.27 3.05 21.2024.26 Actual value 27.19 3.01 21.1124
．． 19 Examples 2 to 7 Synthesis of compounds ■ to '71 The same procedure as in Example 1 was carried out to prepare 0.1 mol of various hydrazinethiol carbamine residual alkali metal salts [1] and various Q
- 0.1 mole of halocarboxylic acid ester [B] is reacted with 100% of various organic solvents to produce various 3-amino-1,3
-thiazolidine-2,4-dione compound was obtained. The results obtained are shown in Table 1. Example 8 Compound compound paste for paint: 3-amino-5-(4-chlorophenyl)-1
- 3-thiazolidine-2,4-dione was blended in the following proportions, thoroughly ground in a pot mill, and mixed to prepare an antifouling paint. (% indicates weight percentage. The same applies hereinafter) Compound of Example 3 20.0% Valve pattern
10.0% talc
15.0% barium sulfate
20.0% vinyl resin
5.5% rosin
5.5% tricresyl phosphate
2.0% methyl isobutyl ketone
11.0% xylene
11.0% total
100.0% Example 9 Compound compound side of paint: 3-amino-5-phenylthio 1,3-thiazolidine-2,4-dione was blended in the following proportions, thoroughly ground in a pot mill, mixed, and made into an antifouling paint. . Example 10 Antifouling test for marine organisms An antifouling test for marine organisms was conducted using antifouling paints prepared in the same manner as in Example 8 using the compounds of the present invention. {1} Preparation of test plate and test method Each steel plate (300xlooo x 1 side) was primed once with wash primer and once with anti-corrosion paint, and each antifouling paint was applied with a brush twice, and crushed. They were fitted into each case, suspended in the sea from a counterfeiting raft, and maintained at a sea depth of 1.5W. '2- Test results As described in '1' above, the painted board immersed in seawater was pulled up at predetermined intervals, and the degree of adhesion of organisms attached to it was expressed as a percentage of the total area of adhesion, as shown in Table 2.
It was shown to. The control was treated with only a wash primer and anti-rust paint. ■ Bay & Unkinu Tachi K: Table 2 Example 11 Antifouling treatment of fishing nets (1) (1' Preparation of resin solution Compound lake: 3-amino-5-(4-chlorophenyl)-1,3-thiazo 1'gin- A resin solution was prepared by blending 2,4-dione in the proportion shown below and thoroughly lighting it. ■ Processing method Polyamide fibers (
An 11-section (3.03 mesh) fishing net made from Toray Industries, Inc. (trade name: Amiran) was soaked, sufficiently impregnated, and then air-dried for one hour for antifouling treatment. Example 12 Antifouling treatment of fishing nets'1) Preparation of resin solution Compound ■: 3-amino-5-phenylthio-1,3-thiazolidine-2,4-dione was blended in the following proportions and thoroughly mixed to prepare a resin solution. . ■ Processing method Example 11 using the resin solution prepared in [11] above.
Antifouling treatment was applied in the same manner as in ■. Example 13 Fishing net treatment and its antifouling test 3-amino-1 synthesized according to the above synthesis examples
An antifouling test was conducted using fishing nets that had been antifouled in the same manner as in Example 11 using each of the 3-thiazolidine-2,4-dione compounds. '1} Test method Cut a test piece into a size of 50 x 50 from each antifouling fishing net, and stretch it on a 60 x 60 arc iron frame.
It will be suspended in the sea from a bond raft and maintained at a depth of 1.5M. ■ Test results As shown in the above tl-, the fishing net submerged in seawater is washed at regular intervals. We observed and measured the adhesion status of seaweed, seaweed, sea lettuce, grass moss, hydro, and seaweed, as well as the weight increase rate of fishing nets. The results are shown in Table-3. The evaluation symbols in this table have the following meanings. - No adhesion at all ± 10 adhesion in spots A small amount of adhesion throughout the entire net A large amount of adhesion throughout the net A large amount of adhesion throughout the entire net, with almost no water permeating Shimodate Also, the weight increase rate of the fishing net is calculated over a given period of time relative to the initial weight of the fishing net. It shows the increase in fishing net weight after the passage of time as a percentage. The weight of these items was determined after the items that had been submerged in the sea were pulled out and drained for 1 hour. Table-3

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. 3-amino-1,3-thiazolidine-2 represented by
・4-dione compound. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (M in the formula indicates an alkali metal atom.) Hydrazinethiol carbamate alkali metal salt, and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 in the formula represents a hydrogen atom, a lower alkyl group, a halogen-substituted phenyl group, or a phenylthio group, R_2 represents a hydrogen atom or a lower alkyl group, R_3 represents a lower alkyl group, and X represents a halogen atom.) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are the same as the groups described above.) 3 -Amino-1,3-thiazolidine-2
- A method for producing a 4-dione compound. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a hydrogen atom, a lower alkyl group, a halogen-substituted phenyl group, or a phenylthio group, and R_2 represents a hydrogen atom or a lower alkyl group.) 3-amino-1,3-thiazolidine-2
- An aquatic organism repellent characterized by containing a 4-dione compound as an active ingredient.