JPS6249260B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel compound ω-fluoropropoxynitrobenzene. The present inventors have been conducting research by synthesizing various compounds in order to obtain effective aquatic organism repellents, but
-Fluoropropoxyaniline was found to have excellent algae-preventing effects. Therefore, ω-fluoropropoxyaniline can be produced using ω-fluoropropoxynitrobenzene as a raw material, and this ω-fluoropropoxynitrobenzene is a new compound with the formula It is indicated by. That is, the present invention is a novel compound ω-fluoropropoxynitrobenzene. The novel compounds ω-fluoropropoxynitrobenzene of the present invention include 2-(ω-fluoropropoxy)nitrobenzene, 3-(ω-fluoropropoxy)nitrobenzene, and 4-(ω-fluoropropoxy)nitrobenzene. Examples of the method for producing the compound of the present invention include the following method. (1) General formula A method of fluorinating ω-substituted propoxynitrobenzene shown by using an alkali fluoride. That is, as the ω-substituted propoxynitrobenzene, the substituent X is Cl, Br, I,

[Formula] -OSO ₂ CH ₃ A compound in which a substituted propoxy group is bonded to any position of the benzene ring is desirable. Furthermore, as the alkali fluoride, potassium fluoride is particularly desirable. However, this reaction causes alkali fluoride to
For ω-substituted propoxynitrobenzene,
Add 1 to 10 times the mole, preferably 4 to 6 times the mole, in water or a commonly used organic solvent.
80-200℃, preferably 130-160℃, 1-
This is carried out by reacting for 20 hours, preferably 6 to 12 hours. (2) Also, a method of fluorinating ω-hydroxypropoxynitrobenzene using α·α-difluoro tertiary amine. That is, examples of ω-hydroxypropoxynitrobenzene include 2-(ω-hydroxypropoxy)nitrobenzene, 3-(ω-hydroxypropoxy)nitrobenzene, and 4-(ω-hydroxypropoxy)nitrobenzene. In addition, as the α・α-difluoro tertiary amine, for example, diethyl (2-chloro-
Examples include 1,1,2-trifluoroethyl)amine, diethyl(1,1,2,3,3-hexafluoropropyl)amine, and the like. Therefore, this reaction is usually carried out at -50 to 100°C, preferably at 20 to 50°C, using stoichiometric amounts of each raw material.
C. for 0.1 to 20 hours, preferably 2 to 6 hours. In addition, when carrying out this reaction, it is preferable to use an organic solvent such as benzene, toluene, xylene, chloroform, carbon tetrachloride, dichloroethane, acetonitrile, benzonitrile, ethyl ether, tetrahydrofuran, etc. in order to carry out the reaction smoothly. . (3) Furthermore, a method of reacting nitrophenol and a fluoropropane derivative in the presence of a base. That is, as nitrophenol, 2-
Nitrophenol, 3-nitrophenol, 4
-Nitrophenol, and the fluoropropane derivatives represented by the formula XCH ₂ CH ₂ CH ₂ F include:
Substituent X is Cl, Br, I,

A compound such as [Formula] -OSO ₂ CH ₃ is desirable. Bases include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkali carbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate, alcoholates such as sodium ethylate, triethylamine, dimethylaniline, and pyridine. Organic and inorganic compounds such as tertiary amines such as Therefore, this reaction is usually carried out using stoichiometric amounts of each raw material at 150°C or lower, preferably at 50°C or lower.
It can be carried out in good yield by reacting at 100°C for 1 to 20 hours, preferably 3 to 7 hours. In addition, during the reaction, for example, water, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, butanol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, etc. It is preferable to use a solvent in order to carry out the reaction smoothly. In this way, ω-fluoropropoxynitrobenzene can be produced. Therefore, this compound is reduced by (a) metals and metal salts such as iron or tin-acidic solution systems and zinc-alkaline solution systems. (b) Reduction with metal hydrogen complex compounds such as aluminum hydride and lithium. (c) Reduction with hydrazine. (d) Catalytic hydrogen reduction using palladium on carbon, etc. By reducing it by a method such as the above, it is possible to obtain ω-fluoropropoxyaniline, which is a highly effective algaecide. Next, an example will be described. Example 1 70 g (0.2 mol) of 3-(γ-p-toluenesulfonylpropoxy)nitrobenzene, 58 g (1 mol) of potassium fluoride, and 10 g (0.02 mol) of hexadecyltributylphosphonium bromide were placed in a Hastelloy 300 ml nutdrive autoclave. , add 60ml of water and 70ml of xylene, and heat to 120℃ for 6 minutes.
The reaction was carried out under heating and stirring for a period of time. After the reaction was completed, the reaction mixture was extracted with toluene, the toluene layer was washed with water and dried over anhydrous sodium sulfate, the toluene was concentrated and distilled off, and the residue was vacuum distilled to obtain 28 g of a pale yellow liquid. The yield was 63% of theory. This product was analyzed by gas chromatography, infrared absorption spectroscopy, nuclear magnetic resonance absorption, etc., and it was found to be 3-(ω-fluoropropoxy)nitrobenzene.

[Table] Example 2 In a flask equipped with a thermometer and a stirrer, 4-
(ω-hydroxypropoxy)nitrobenzene
19.7g (0.1 mol), diethyl (2-chloro-1.
1,2-trifluoroethyl)amine 19g (0.1
mol) and 50 ml of dichloromethane were taken and reacted with stirring at room temperature for 5 hours. After the reaction is complete, cool the reaction mixture.
After washing with 10% potassium carbonate aqueous solution and water,
Dry over anhydrous sodium sulfate, concentrate and distill off dichloroethane, and vacuum distill the residue to obtain 11 g of pale yellow liquid.
I got it. The yield was 56% based on the theoretical amount.
As a result of analyzing this product in the same manner as in Example 1, 4-
It was confirmed that it was (ω-fluoropropoxy)nitrobenzene.

[Table] Example 3 In a flask equipped with a thermometer, reflux condenser, and stirrer, 27.8 g (0.2 mol) of 3-nitrophenol,
Potassium carbonate 13.8g (0.2mol), 1-bromo-3
- 29 g (0.2 mol) of fluoropropane and 50 ml of acetonitrile were charged, and the mixture was reacted with stirring under heating under reflux for 4 hours. After the reaction is complete, the precipitate is filtered off, the acetonitrile is concentrated and distilled off, and the residue is dissolved in benzene.
After washing in the order of water - dilute aqueous sodium hydroxide solution - water, it was dried over anhydrous sodium sulfate, the benzene was concentrated and distilled off, and the residue was vacuum distilled to form a pale yellow liquid.
36.6g was obtained. The yield was 92% based on the theoretical amount. As a result of analyzing this product in the same manner as in Example 1, it was found to be 3-(ω-fluoropropoxy)nitrobenzene. (Reference Example) The effect as an algaecide of 3-(ω-fluoropropoxy)aniline produced using the ω-fluoropropoxynitrobenzene of the present invention as a raw material is shown. That is, 80 ml of seawater containing 500 to 1000 Enteromorpha compressa spores per ml is dispensed into a 100 ml flat culture flask, and each test compound is added to the predetermined concentration. It dissolved like this. The culture flasks thus treated were kept at 20 °C.
Place it in a place illuminated with 300 lux using a white fluorescent lamp, and proceed with the culture while blowing air into the culture solution at a rate of 200 to 300 ml per minute, and it will adhere to the culture flask wall over time. We observed the state of attachment and elongation of Enteromorpha compressor. The results are shown in the table below. The state of adhesion and extension was determined according to the following criteria. (Judgment criteria) −: No growth ±: Signs of growth +: Growth area is 1/3 or less of the flask wall 〃 〃 About 1/3〓: 〃 〃 1/3 or more

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Claims (1)

[Claims] 1 formula ω-fluoropropoxynitrobenzene represented by