JP3695782B2 - Disulfide compound - Google Patents

Description

【００５２】
上記応用例の結果から明らかなように、本発明のジスルフィド化合物（アルキル−置換メチルジスルフィド化合物）は、水中有害生物に対して強い忌避活性または抗生物活性を示し、水中有害生物防除剤として極めて顕著な効果を示し、従来使用されている水中有害生物防除剤（比較例３および４）と比較しても極めて顕著な効果を示す（応用例１〜１１）。
また、置換基を持たないアルキル−メチルジスルフィド用した場合にはその効果は全く見られず（比較例２）、本発明の特定の置換基を有する化合物の効果が極めて特異的なものであることが明らかである。
【００５３】
【発明の効果】
本発明のジスルフィド化合物は、強い生物忌避活性または抗生物活性を示すものである。
また、本発明のジスルフィド化合物は、安全衛生、環境面での問題点、即ち人体に対する毒性や残留性などが低く、生態系や作業環境に悪影響を及ぼすことがなく、しかも、水中有害生物の防除効果を長期間発揮しえる水中有害生物防除剤として有用である。
更に、本発明のジスルフィド化合物は、スライム防止剤、殺菌剤、抗菌剤、農薬、医薬等として有用である。[0001]
[Industrial application fields]
The present invention relates to an aquatic pest control agent, a slime inhibitor, a bactericidal agent, an antibacterial agent, an agrochemical, a pharmaceutical and the like useful for the prevention of damage caused by the adhesion and propagation of pests in seawater or industrial water systems. It relates to substituted methyl disulfide compounds.
[0002]
[Prior art and problems to be solved by the invention]
Large attachments such as barnacles, mussels, and seaweeds to underwater structures such as ships, port facilities, buoys, pipelines, bridges, offshore oilfield drilling equipment, waterway pipes of power plants or coastal plants, fishing nets and aquaculture rods Plants and animals, diatoms, bacteria and other micro-organisms adhere to the structure, damage the structure, increase the marine frictional resistance of the ship, clogging the fishing net, kill fish and shellfish, cause sedimentation and decrease work efficiency due to increased weight. appear. In addition, in industrial water systems such as cooling water using natural water such as river water and lake water, and in circulation cooling devices using middle and tap water, bacteria, diatoms, cyanobacteria, and blue waters grow abnormally, resulting in poor water quality. It causes problems such as deterioration of cooling efficiency due to deterioration and adhesion to the vessel wall, blockage of water pipes, and reduction of flow rate.
[0003]
In order to prevent such damage caused by pests in water, inorganic heavy metal compounds such as cuprous oxide, rhodanide, mercury oxide, or tributyltin oxide, triphenyltin oxide, tributyltin (meth) acrylate polymer, etc. An antifouling agent containing an organometallic compound is used.
[0004]
However, these conventionally used compounds are extremely toxic to the human body and not only require special handling, but also cause problems such as malformation due to accumulation in fish and environmental pollution. There has been a demand for using an antifouling agent containing no metal.
[0005]
As antifouling agents containing no heavy metals or organic metals, various compounds containing sulfur atoms such as thiuram compounds, benzothiazole compounds, and thiocyan compounds have been proposed, but their effects are still insufficient. JP-A-60-38306 proposes to use a dialkyl polysulfide compound in combination with other compounds having a control action as an antifouling agent for fishing nets. As such, the compound has no bioactive effect.
[0006]
Accordingly, the object of the present invention is to provide safety and health and environmental problems, i.e., low toxicity and persistence to the human body, no adverse effects on the ecosystem and work environment, and the effect of controlling pests in water. It is an object of the present invention to provide a compound useful as an underwater pest control agent capable of exhibiting a long-term effect.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that a specific disulfide compound has a strong repellent activity and / or antibiotic activity against the above-mentioned aquatic pests.
[0008]
The present invention has been made based on the above findings, and provides a disulfide compound represented by the following general formula (I).
[0009]
R—S—S—CH ₂ —X (I)
(In the formula, R represents an alkyl group having 4 to 18 carbon atoms, and X represents a chlorine atom, a bromine atom, an iodine atom, or -SCN.)
[0010]
The disulfide compound of the present invention is a disulfide compound (alkyl-substituted methyl disulfide compound) represented by the above general formula (I), and has excellent biological repellent activity and / or antibiotic activity. It is useful not only as a pest control agent, but also as a slime inhibitor, bactericidal agent, antibacterial agent, agricultural chemical, pharmaceutical, and the like.
[0011]
In the disulfide compound represented by the general formula (I), examples of the alkyl group having 4 to 18 carbon atoms represented by R include butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, heptyl, Examples include linear or branched alkyl groups such as octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tertiary dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, etc. et al are.
[0012]
Accordingly, examples of the disulfide compound represented by the general formula (I) include the following compounds 1 to 11.
[0013]
Compound 1 nC ₈ H ₁₇ -SS-CH ₂ -Cl
[0014]
Compound 2 tC ₈ H ₁₇ -SS-CH ₂ -Cl
[0015]
Compound 3 tC ₉ H ₁₉ -SS-CH ₂ -Cl
[0016]
Compound 4 nC ₁₂ H ₂₅ -SS-CH ₂ -Cl
[0017]
Compound 5 tC ₁₂ H ₂₅ -SS-CH ₂ -Cl
[0018]
Compound 6 nC ₄ H ₉ -SS-CH ₂ -Cl
[0019]
Compound 7 nC ₈ H ₁₇ -SS-CH ₂ -SCN
[0020]
Compound 8 tC ₈ H ₁₇ -SS-CH ₂ -SCN
[0021]
Compound 9 tC ₉ H ₁₉ -SS-CH ₂ -SCN
[0022]
Compound 10 nC ₁₂ H ₂₅ -SS-CH ₂ -SCN
[0023]
Compound 11 tC ₁₂ H ₂₅ -SS-CH ₂ -SCN
[0024]
Among the disulfide compounds represented by the above general formula (I), a compound in which X is a chlorine atom, a bromine atom or an iodine atom can be produced, for example, by reacting an alkyl mercaptan with a methyl thiocyanate halide. A compound in which X is —SCN can be easily produced by reacting the compound in which X is a chlorine atom, bromine atom or iodine atom with an alkali thiocyanate.
[0025]
【Example】
Next, specific synthesis examples (examples) of the disulfide compound of the present invention (disulfide compound represented by the above general formula (I)) will be shown, but the present invention is not limited by these synthesis examples. . The following synthesis examples are synthesis examples of the compounds 1 to 11 listed above as examples of the sulfide compound represented by the general formula (I).
[0026]
Example 1 (Synthesis of Compound 1)
Into the flask, 14.6 g of n-octyl mercaptan, 10.7 g of methyl thiocyanate, 20 g of acetone and 14 g of anhydrous potassium carbonate were charged and reacted under reflux of acetone for 5 hours. The insoluble matter produced by filtration was removed, and after acetone was removed by an evaporator, 10.5 g of a light yellow liquid fraction of 150 ° C./12 mmHg was obtained by distillation under reduced pressure.
[0027]
Result of IR spectrum was measured of the product, 2940,2910 and 2840cm ^-1 absorption based on the alkyl group is seen, absorption based on C-S bonds to 650 cm ^-1 was observed, C-Cl bonds to 700 cm ^-1 As a result of mass spectrum analysis, m / z = 226, and from H ¹ -NMR, 4.7 ppm (s) 2 H, 2.9 ppm (t) 2 H, 2.6 to 0.6 ppm (M) Since absorption was observed in 15H, it was confirmed that it was the target compound 1.
[0028]
Example 2 (Synthesis of Compound 2)
9.8 g of a pale yellow liquid fraction having a boiling point of 70 ° C./0.23 mmHg was obtained in the same manner as in Example 1 except that 14.6 g of tertiary octyl mercaptan was used instead of n-octyl mercaptan.
[0029]
As a result of measuring the IR spectrum of the product, there was absorption at 2950, 2900, 2870, 1463, 1360, 1258, 1218, 1100, 1015, 797, 705 and 650 cm ⁻¹ , and from NMR, 4.68 ppm (s ) 2H, 1.7 ppm (s) 2 H, 1.46 ppm (s) 6 H, and 0.97 ppm (s) 9 H, absorption was confirmed, confirming that compound 2 was the target compound.
[0030]
Example 3 (Synthesis of Compound 3)
A 16.8 g fraction of a pale yellow liquid having a boiling point of 78 ° C./0.22 mmHg was obtained in the same manner as in Example 1 except that 16.0 g of tert-nonyl mercaptan was used instead of n-octyl mercaptan.
[0031]
As a result of measuring the IR spectrum of the product, absorption was found at 2960, 2925, 2870, 1458, 1378, 1217, 1123, 837, 705 and 650 cm ⁻¹ , and from NMR, 4.63 ppm (s) 2 H and 0 Since absorption was observed at .58 to 1.97 ppm (m) 19H, it was confirmed to be the target compound 3.
[0032]
Example 4 (Synthesis of Compound 4)
The reaction was carried out in the same manner as in Example 1 except that 20.2 g of n-dodecyl mercaptan was used instead of n-octyl mercaptan. After removing the insoluble matter produced by filtration and deacetoneating with an evaporator, the product was purified with a silica gel column using n-hexane as a developing solvent to obtain 19.7 g of a pale yellow liquid product.
[0033]
As a result of measuring the IR spectrum of the product, absorption was observed at 2920, 2845, 1460, 1217, 703 and 650 cm ⁻¹ , which confirmed that it was the target compound 4.
[0034]
Example 5 (Synthesis of Compound 5)
19.7 g of a pale yellow liquid product was obtained in the same manner as in Example 4 except that 20.2 g of tertiary dodecyl mercaptan was used instead of n-dodecyl mercaptan.
[0035]
As a result of measuring the IR spectrum of the product, absorption was observed at 2950, 2920, 2860, 1455, 1375, 1210, 1140, 830, 700, 650 and 585 cm ⁻¹ , confirming that it was the target compound 5 did.
[0036]
Example 6 (Synthesis of Compound 6)
11.9 g of a light yellow liquid fraction having a boiling point of 73 ° C./4 mmHg was obtained in the same manner as in Example 1 except that 9.0 g of n-butyl mercaptan was used instead of n-octyl mercaptan.
[0037]
As a result of measuring the IR spectrum of the product, absorption was observed at 2960, 2930, 2870, 1460, 1380, 1218, 840, 710 and 655 cm ⁻¹ .
[0038]
Example 7 (Synthesis of Compound 7)
The compound 1, 11.3 g obtained in Example 1, 8.1 g of sodium thiocyanate and 50 g of acetone were taken and reacted under reflux for 30 hours. After removing the insoluble matter produced by filtration and deacetoneating with an evaporator, the product was purified with a silica gel column using chloroform / n-hexane (1/3) as a developing solvent to obtain 4.3 g of a pale yellow liquid product.
[0039]
Result of IR spectrum of the product was measured, and loss absorption based on C-Cl bonds 700 cm ^-1, absorption is expressed based on the CN binds to 2150 cm ^-1, the result m / z = 249 Mass spectral analysis, In addition, absorption was observed at 4.2 ppm (s) 2 H, 2.9 ppm (t) 2 H, 1.9 to 0.7 ppm (m) 15 H from H ¹ -NMR. I confirmed that there was.
[0040]
Example 8 (Synthesis of Compound 8)
7.6 g of a pale yellow liquid product was obtained in the same manner as in Example 7, except that Compound 2 was used instead of Compound 1.
[0041]
As a result of measuring the IR spectrum of the product, there was absorption at 2940, 2900, 2860, 2150, 1462, 1358, 1188, 1100, 977, 825 and 685 cm ⁻¹ , and 4.17 ppm (s) 2 H from NMR. 1.67 ppm (s) 2H, 1.46 ppm (s) 6H, and 1.04 ppm (s) 9H were confirmed to be the target compound 8.
[0042]
Example 9 (Synthesis of Compound 9)
9.1 g of a pale yellow liquid product was obtained in the same manner as in Example 7, except that 12.0 g of compound 3 was used instead of compound 1.
[0043]
As a result of measuring the IR spectrum of the product, absorption was observed at 2950, 2920, 2850, 2150, 1460, 1370, 1190, 825 and 690 cm ⁻¹ , which confirmed that it was the target compound 9.
[0044]
Example 10 (Synthesis of Compound 10)
9.7 g of a pale yellow liquid product was obtained in the same manner as in Example 7, except that 12.7 g of Compound 4 was used instead of Compound 1.
[0045]
As a result of measuring the IR spectrum of the product, absorption was observed at 2950, 2920, 2850, 2150, 1460, 1375, 1192, 828 and 693 cm ⁻¹ , which confirmed that it was the target compound 10.
[0046]
Example 11 (Synthesis of Compound 11)
10.2 g of a pale yellow liquid product was obtained in the same manner as in Example 7, except that 12.7 g of compound 5 was used instead of compound 1.
[0047]
Result of IR spectrum of the product was measured, absorption based on C-Cl bonds 700 cm ^-1 observed in Compound 5 of the raw material disappeared, the absorption is expressed based on the CN binds to 2150 cm ^-1, mass spectral analysis As a result, m / z = 305, and from H ¹ -NMR, absorption was observed at 4.1 ppm (s) 2 H, 2.1 to 0.4 ppm (m) 25 H. I confirmed that there was.
[0048]
As described above, the disulfide compound of the present invention is useful as an underwater pest control agent, anti-slime agent, bactericidal agent, antibacterial agent, agricultural chemical, pharmaceutical, etc., but in the following application examples, the disulfide compound of the present invention is used. The effect when used as an underwater pest control agent is shown.
[0049]
Application Example After adding 20 parts by weight of the sample compound shown in Table 1 below to 100 parts by weight of a 30% xylene solution of chlorinated rubber having 65% chlorine content (CR-20 manufactured by Asahi Denka Kogyo Co., Ltd.) and stirring sufficiently The test piece was coated on a hard vinyl chloride plate and dried for 24 hours.
[0050]
This test piece was immersed in a depth of 1 m in the sea with a test pad in Yokosuka City, Kanagawa Prefecture, and the degree of fouling by attached organisms was observed over time, and the ratio of the adhered area to the painted area was measured. The results were evaluated in four stages according to the following criteria, and the results are shown in [Table 1] below.
A: Adhesion was not recognized at all.
B: Adhesion was observed in a portion of 50% or less.
C: Adhesion was observed in 50% or more.
D: Adhered to the entire surface, and the painted surface was completely covered.
[0051]
[Table 1]

[0052]
As is clear from the results of the above application examples, the disulfide compound (alkyl-substituted methyl disulfide compound) of the present invention exhibits a strong repellent activity or antibiotic activity against aquatic pests and is extremely remarkable as an aquatic pest control agent. Even when compared with conventionally used aquatic pest control agents (Comparative Examples 3 and 4), it shows extremely remarkable effects (Application Examples 1 to 11).
Further, when alkyl-methyl disulfide having no substituent is used, the effect is not seen at all (Comparative Example 2), and the effect of the compound having a specific substituent of the present invention is extremely specific. Is clear.
[0053]
【The invention's effect】
The disulfide compound of the present invention exhibits strong biological repellent activity or antibiotic activity.
In addition, the disulfide compound of the present invention has low safety and health and environmental problems, that is, low toxicity and persistence to the human body, does not adversely affect the ecosystem and work environment, and also controls aquatic pests. It is useful as an underwater pest control agent that can exert its effect for a long time.
Furthermore, the disulfide compound of the present invention is useful as an anti-slime agent, a bactericidal agent, an antibacterial agent, an agrochemical, a pharmaceutical and the like.

Claims (1)

A disulfide compound represented by the following general formula (I).
R—S—S—CH ₂ —X (I)
(In the formula, R represents an alkyl group having 4 to 18 carbon atoms, and X represents a chlorine atom, a bromine atom, an iodine atom or —SCN.)