JPS6227057B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to substituted naphthylmethyl propiolate compounds, which are novel compounds that have not yet been described in the literature. Places that are in constant contact with seawater, such as the bottoms of ships, fishing nets, buoys, and other equipment placed in seawater, underwater structures such as dam attachments, and intake channels for condenser cooling water in thermal power plants, are covered with green laver. , seaweed such as sea lettuce, seaweed, barnacle, mussel, sea squirt, etc.
Irrigation ponds, ornamental fish ponds, etc. where shellfish and fresh water are used.
Cooling towers, etc., have adherent and propagated algae, causing economic losses and aesthetic defects in ornamental fish ponds. For example, in ships, it not only causes an increase in navigation speed and fuel consumption, but also causes economic losses due to the cost of cleaning the bottom of the ship or the suspension of operations during the cleaning period. This will cause inconvenience in handling and operation, and the amount of water taken in water intake devices such as condensers and heat exchangers will decrease, resulting in a decrease in cooling efficiency.
The detached biomass causes a decline in the performance of equipment. Due to shellfish algae growing in aquaculture fishing nets,
There are many examples of the economic losses caused by oxygen deprivation, fish mortality due to disease, and reduced growth rates. Therefore, in order to prevent problems caused by attached breeding of seawater and freshwater harmful organisms, organic tin compounds such as tributyltin oxide, organic chlorine compounds such as pentachlorophenol, and methylene bisthiocyanate have been used. Organic sulfur-based compounds such as chlorine, etc. were used in paints, etc., and chlorine, formalin, etc. were added directly to cooling water intake channels. However, although these conventional aquatic organism repellents are sufficiently effective depending on the purpose or season, they corrode the coating material. Moreover, it is not necessarily satisfactory in terms of practical odor and toxicity to the human body. In order to solve this problem, the present inventors synthesized various compounds, investigated the effects on harmful attached organisms, and as a result of extensive research, we created a novel substituted naphthyl methyl propiolate compound represented by the following formula. was found to be useful as an aquatic organism repellent, and its effectiveness was superior to that of conventional propiolic acid esters such as substituted benzyl propiolate described in Japanese Patent Publication No. 48-23902, leading to the completion of the present invention. Ivy. The novel substituted naphthyl methyl propiolate compounds of the present invention have the general formula (In the formula, X represents a hydrogen atom, a halogen atom, or a lower alkyl group, Y represents a hydrogen atom or a halogen atom, and Z represents a hydrogen atom or a lower alkyl group.) Examples of the novel substituted naphthylmethyl propiolate compounds of the present invention include the following. (1) 1-Naphthylmethylpropiolate (2) 2-Naphthylmethylpropiolate (3) (4-chloro-1-naphthylmethyl)propiolate (4) (1-bromo-2-naphthylmethyl)propiolate (5) ) (6-Methyl-2-naphthylmethyl) propiolate (6) (3-methyl-2-naphthylmethyl) propiolate (7) (4-bromo-3-methyl-1-naphthylmethyl) propiolate Novel substituted naphthyl of the present invention The methylpropiolate compound has the general formula [] in an organic solvent. (In the formula, A represents a halogen atom, and X, Y and Z represent the same meanings as above.) A halogenomethylnaphthalene compound represented by the general formula [] (In the formula, M represents an alkali metal atom.) It is synthesized by reacting with an alkali metal salt of propiolic acid represented by the following by a conventional method. In addition, the novel substituted naphthyl propiolate compound of the present invention can be prepared with the general formula [] in the presence of an acid catalyst in an organic solvent. (In the formula, X, Y and Z represent the same meanings as above.) It can also be synthesized by reacting a substituted naphthalene methanol compound represented by the following with propiolic acid by a conventional method. The novel compound of the present invention can be used as an aquatic organism repellent, an antibacterial agent, and the like. In order to use the novel compound of the present invention as an aquatic organism repellent, it can be applied by dispersing it in water as an emulsion or hydrating agent, or by incorporating it into a paint.
can be used. Next, an example will be described. Example 1 (Synthesis Example) Synthesis of 1-naphthylmethylpropiolate A 300 ml reaction flask equipped with a Dimroth condenser was charged with 17.7 g of 1-chloromethylnaphthalene, 10.8 g of propiolic acid potassium salt, and 100 ml of dimethylformamide. The reaction was carried out at 80° C. for 4 hours while stirring. After the reaction was completed, the reaction solution was poured into water, extracted with benzene, dried, concentrated, and distilled under reduced pressure to obtain 1-naphthylmethylpropiolate (

[Formula] Colorless viscous liquid, boiling point 105-113℃/0.01mmHg, n ²⁰ _D 1.6040) 9.1g
(yield 40.6%). The compounds were identified by gas chromatography, infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc. Example 2 (Synthesis Example) Synthesis of 2-naphthylmethylpropiolate In a 300 ml reaction flask equipped with a Dean Stark apparatus, 15.8 g of 2-naphthalene methanol, 7.7 g of propiolic acid, and p-toluenesulfonic acid were added. Add 0.9g and 100ml of benzene,
The reaction was carried out with stirring and reflux while azeotropically removing the produced water, and the reaction was terminated when 1.8 ml of produced water was obtained. After the reaction was completed, the reaction solution was washed with sodium bicarbonate and water, dried and concentrated, and the obtained solid was reconsolidated with methanol to give 2-naphthylmethylpropioleate (

[Formula] Colorless powder, melting point 90.0-92.5°C) 4.7g (yield 21.0%) was obtained. Example 3 (Synthesis example) Synthesis of (4-chloro-1-naphthylmethyl) propiolate Same as Example 1 except that 21.1 g of 1-chloro-4-chloromethylnaphthalene was used instead of 1-chloromethylnaphthalene. (4-chloro-1-naphthylmethyl)propiolate (

[Formula] Colorless acicular crystals, boiling point 99-103℃/0.015mmHg, melting point 67.0-68.5℃)
8.5 g (yield 34.8%) was obtained. Example 4 (Synthesis example) Synthesis of (1-bromo-2-naphthylmethyl) propiolate Same as Example 1 except that 30.0 g of 1-bromo-2-bromomethylnaphthalene was used instead of 1-chloromethylnaphthalene. (1-bromo-2-naphthylmethyl)propiolate (

[Formula] 12.0 g (yield 41.5%) of colorless powder (melting point 59.0-61.0°C) was obtained. Example 5 (Synthesis example) Synthesis of (6-methyl-2-naphthylmethyl) propiolate (Instead of 1-chloromethylnaphthalene, 6-
(6-Methyl-2-naphthylmethylpropiolate (6-methyl-2-naphthylmethylpropiolet)

[Formula] 19.9 g (yield 88.8%) of colorless powder (melting point 93.0-95.0°C) was obtained. Example 6 (Synthesis example) Synthesis of (3-methyl-2-naphthylmethyl) propiolate Same as Example 1 except that 23.5 g of 3-methyl-2-bromomethylnaphthalene was used instead of 1-chloromethylnaphthalene. (3-methyl-2-naphthylmethyl) propiolate (

[Formula] 20.3 g (yield 90.6%) of colorless powder (melting point 85.0-87.0°C) was obtained. Example 7 (Synthesis example) Synthesis of (4-bromo-3-methyl-1-naphthylmethyl) propiolate 4-bromo-3-methyl-1-chloromethylnaphthalene was used instead of 1-chloromethylnaphthalene.
(4-Bromo-3-methyl-1-naphthylmethyl) propiolate (4-bromo-3-methyl-1-naphthylmethyl) propiolate (

[Formula] Colorless viscous liquid Boiling point 141-150℃/0.015mmHgn ²⁰ _D 1.6272) 21.6g
(yield 71.3%). Example 8 (Effect on harmful shellfish) The effect on barnacles, which cause the greatest inhibition among harmful shellfish, was investigated. Pour 3 ml of seawater into a graduated cylinder, add 10 sessile-stage Keeprius larvae of Vertical Barnacle within 24 hours after moulting, and then add 4 ml of seawater to the volume. Transfer this to a glass tray with a diameter of 3 cm and a depth of 1 cm. 2% of the compound of the present invention, 90% of cyclohexanone
%, Tween-80 8% is diluted with seawater to a predetermined concentration, and 1 ml of this is added to a shear dish to make the concentration of the seawater in which the sessile stage larvae, Keeprius, swim, to be 1 ppm and 0.5 ppm. In this case, 1
There will be three siyares per ward. Close the lid and leave it in a constant temperature room at 20℃ for 24 hours.
After some time, the survival rate of Keypurius was investigated. Also, as a comparative example, Deldrin,
Similar tests were conducted using 4-fluorobenzylpropiolate (abbreviated as 4FBP in the table) and 2-methylbenzylpropiolate (abbreviated as 2MBP in the table) described in the specification of No. 23902. Ivy. The results are shown in Table 1.

[Table] Example 9 (Effect on harmful algae) 78 ml of seawater containing 100 to 150 spores/ml of A. spores was placed in a 100 ml flat culture flask, and the emulsion of the compound of the present invention described in Example 8 was added to the seawater. Dilute to a predetermined concentration and add 2 ml to make the concentration of the compound of the present invention in seawater in the flask 5 ppm. The flask treated in this way was fixed at a temperature of 20°C and illuminated with white fluorescent light at 3000 lux.
Aerate at 10 to 150 c.c./min from the bottom of the flask using a glass capillary. After culturing in this manner for 10 days, it was possible to observe the growth of the green aonori adhering to the flask wall over time. In addition, as comparative examples, tributyltin oxide (abbreviated as TBTO in the table), 4-fluorobenzylpropiolate (abbreviated as 4FBP in the table) described in Japanese Patent Publication No. 48-23902, and 2-methylbenzylpropiolate (abbreviated as 2MBP in the table) was also used in a similar test. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X represents a hydrogen atom, a halogen atom, or a lower alkyl group, Y represents a hydrogen atom or a halogen atom, and Z represents a hydrogen atom or a lower alkyl group.) .