JPS6328905B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 2-dimethylamino-1,3-dithiocyanatopropane (2), which is characterized by reacting 2-dimethylamino-1,3-bis(alesulfonylthio)propane (2) with a cyanide salt. It concerns the manufacturing method. The target compound of the present invention () is a compound known in the literature, and it is stated in Japanese Patent Publication No. 51-42177 that this compound itself has a strong insecticidal and acaricidal action. It is stated in Japanese Patent Publication No. 42-10969 that it is an important intermediate in the production of thiol carbamate derivatives that have insecticidal activity. Regarding the production method of this compound, a method of reacting a thiocyanate (rhodanate) with the corresponding dihalide compound is described in Japanese Patent Publication No. 18012/1973, and a method of reacting a cyanide with the corresponding thiosulfate salt (Bunte salt). A method is described in Japanese Patent Publication No. 44-19524, and a method of reacting a corresponding dithiol compound with a cyanogen halide is described in Japanese Patent Publication No. 47-34316. The present inventors have continued their intensive research in order to explore and develop a method for producing the target compound () even more easily, with higher purity, and with higher yield. It was discovered that () was produced in a surprisingly good yield, and based on this, the present invention was completed. (), which is the starting material compound of the present invention, is a compound known in the literature, and its production method is such that it can be easily produced with high purity and high purity by reacting the corresponding dichloride compound with allenethiosulfonate. The fact that it could be produced with high yield was recognized
18847, and that this compound itself also has a strong insecticidal effect, as reported in Japanese Patent Publication No. 46-13755.
It is stated in However, little is known about the chemical reactions of this compound (2) with various reagents, and it is believed that 4-dimethylamino-1,2-dithiolane can be obtained by treating it with a basic substance.
15261. When the present inventors reacted the compound () with cyanide, which can be said to be a type of basic substance, a chemical reaction completely different from that described above was observed, and the reaction proceeded smoothly under extremely mild conditions and in a short time. It was found that the target compound, the dithiocyanate derivative (), was obtained in quantitative yield. Furthermore, the allene sulfinate by-produced by the reaction of the present invention is water-soluble and can be easily separated from the main product, the fat-soluble target compound (), after the reaction is completed. For example, when water is used as the reaction solvent, by separating the main product and concentrating the aqueous mother liquor to dryness, allene sulfinate can be quantitatively recovered as a high-purity product. This allene sulfinate can be easily regenerated into allenethiosulfonate, which is the raw material for the raw material compound (), by treating it with sulfur in the presence of an amine, for example. Therefore, in the reaction of the present invention, there are no combustion wastes to be produced, and the production method can be said to be extremely advantageous from the viewpoint of pollution prevention measures and resource saving. Allen in the raw material compound () used in the present invention is, for example, an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, cumene, naphthalene, etc., and furthermore, for example, halogen (chloro, brome, etc.), nitro, acetylamino,
Aromatic hydrocarbons substituted with lower alkoxy (methoxy, ethoxy, etc.), lower alkylthio (methylthio, ethylthio, etc.), such as chlorobenzene, dichlorobenzene, bromobenzene, nitrobenzene, acetamidobenzene, methoxybenzene, methylthiobenzene, etc. It's okay. Specific raw materials () used in the present invention include (1) 2-dimethylamino-1,3-bis(benzenesulfonylthio)propane, mp83-4°C (2) 2-dimethylamino-1,3-bis (2-Methylbenzenesulfonylthio)propane oxalate, mp131~2℃ (decomposition) (3) 2-dimethylamino-1,3-bis(4-methylbenzenesulfonylthio)propane, m.
p.114～5℃ (4) 2-dimethylamino-1,3-bis(4-chlorobenzenesulfonylthio)propane, m.
p.143～4℃ (5) 2-dimethylamino-1,3-bis(4-methoxybenzenesulfonylthio)propane,
mp115.5～7℃ (6) 2-dimethylamino-1,3-bis(β-naphthalenesulfonylthio)propane, mp110
-5℃ etc. The cyanide used in the present invention may be a solid alkali metal salt of cyanide such as sodium cyanide or potassium cyanide, which is usually easily available as a commercial product, and if desired, an ammonium salt or an alkaline earth metal salt, Heavy metal salts can also be used. This reaction progresses quantitatively within a short time, so
The amount of cyanide necessary for the reaction is stoichiometrically sufficient to be 2 moles exactly corresponding to 1 mole of the starting compound (), and a slight excess may be used if desired. Excessive use is undesirable from the viewpoint of saving resources and treating the eruption solution after the reaction. As the solvent used in the reaction of the present invention, a solvent capable of dissolving one or both of the raw material compound () and the cyanide salt is preferable, but the reaction proceeds satisfactorily even if it is a solvent in which both are difficult to dissolve. However, solvents whose liquid properties tend to be extremely acidic or alkaline are unfavorable due to the properties of the reagent or the properties of the raw materials and target compounds () and (). Therefore, as long as the solvent is approximately neutral, as long as it does not inhibit the reaction. Any solvent can be used.
That is, examples of the solvent include lower aliphatic alcohols such as methanol, ethanol, and isopropanol, lower aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and lower chain or cyclic aliphatic substances such as diethyl ether, tetrahydrofuran, and dioxane. Group ethers such as lower aliphatic carboxylic acid derivatives such as ethyl acetate, acetonitrile and dimethylformamide, lower chain or cycloaliphatic sulfur compounds such as carbon disulfide, dimethyl sulfoxide and tetramethylene sulfone, etc. can be used. If desired, water, lower aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene may also be used. . Each of these solvents may be used alone, or two or more solvents may be used as a mixture at an appropriate mixing ratio. Furthermore, when a mutually immiscible combination is used, for example, a combination of water and an aromatic hydrocarbon or an aliphatic halogenated hydrocarbon, a two-layer system is formed; in such a case, a quaternary ammonium salt, Favorable results can be obtained by adding a small amount of a so-called phase transfer catalyst such as a sulfonium salt or a phosphonium salt. The reaction of the present invention starts immediately by bringing the raw material compound (2) into contact with the cyanide salt in a solvent, and is even exothermic in some cases. The product, the target compound (), is a solid with a low melting point in its free base state and is unstable to heat, so it is desirable to keep the reaction temperature below 45°C, usually at room temperature. It is preferable to keep it at or below that level. Therefore, it may even be necessary to cool the reaction vessel externally. Further, the reaction of the present invention proceeds very smoothly under the above conditions and is usually completed within several hours, but may be completed within several minutes to more than ten minutes in some cases. The target compound (), which is the product, also lacks stability against alkalis, so the reaction time is unnecessarily extended and it is left in contact with excess cyanide ions and by-produced allenesulfinate ions for a long time. Leaving it for a while may cause coloration and decrease in yield, which is disadvantageous, so immediately after the reaction is completed, the reaction system should be cooled to promote crystal precipitation, or isolated from the reaction system by extraction and transfer into a soluble solvent. is desirable. The completion of this reaction is the precipitation of the generated target compound () out of the system or thin layer chromatography (TLC).
It can be easily confirmed by instrumental analysis methods such as high-performance liquid chromatography (HLC). The target compound () produced by the production method of the present invention has sufficiently high purity even in its crude form, and can be used as a production intermediate as it is, but if desired, it may be purified by recrystallization from an appropriate solvent. In some cases, it is also possible to secure stability as an organic or inorganic acid salt and then purify it by recrystallization. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 Sodium cyanide (sodium cyanide) in 50ml of water
Dissolve 2.2g (95% purity, 0.042 mol) and add 2-dimethylamino-1, 2-dimethylamino-1, while stirring at room temperature.
3-bis(benzenesulfonylthio)propane
Add 8.6g (0.02mol) little by little. During this time, it generates a little heat and the internal temperature rises by about 2 degrees Celsius. As it is,
After continuing stirring at room temperature for about 1 hour, the reaction vessel was cooled with ice water to lower the internal temperature to 10°C. The precipitated white crystalline powder is collected by filtration, washed with a small amount of water, and dried in a desiccator under reduced pressure. The yield is
3.8 g (95%) showed a melting point of 50 to 52°C, which was consistent with the separately synthesized standard 2-dimethylamino-1,3-dithiocyanatopropane. The reaction mother liquor was concentrated to dryness under reduced pressure to obtain 7.0 g of white crystals. When this was compared with a separately prepared standard sodium benzenesulfinate (dihydrate) using high performance liquid chromatography, the purity was 91.5%.
Therefore, the recovery rate was 97%. A reaction was carried out according to Example 1 above, and the results shown in the following table were obtained.

[Table] *2 Nitrogen gas was bubbled throughout the reaction.

Claims (1)

[Claims] 1 2-dimethylamino-1,3 characterized by reacting 2-dimethylamino-1,3-bis(alesulfonylthio)propane with a cyanide salt
- A method for producing dithiocyanate propane.