JPS6257194B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel phosphonomethylaminosulfinyl chloride derivative and a method for producing the same. The compound of the present invention, amines, alcohols,
Compounds obtained by reacting with phenols and thiophenols are excellent as active ingredients for herbicides. For example, the applicant has already applied for a reaction product between the compound of the present invention and a phenol or thiophenol, and a herbicide containing the product as an active ingredient. Therefore, the compounds of the present invention are useful as intermediate raw materials for herbicides. The compounds of the present invention have the general formula (R ₁ and R ₂ represent alkyl or phenyl. R ₃ represents cyanomethyl or alkoxycarbonylmethyl), and is a new compound that has not been described in any literature. The alkyl in R ₁ and R ₂ above is preferably one having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl. The alkoxycarbonylmethyl for R ₃ is preferably one having 3 to 8 carbon atoms, such as methoxycarbonylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl. Compounds of the invention may have the general formula It can be easily obtained by reacting the phosphonomethylamine derivative represented by (R ₁ to _{R 3} are the same as above) with thionyl chloride. The reaction between the compound of formula [] and thionyl chloride is carried out without a solvent or in a suitable solvent. Examples of the solvent include halogenated hydrocarbons such as methyl chloride, chloroform, and carbon tetrachloride, and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane. formula〔〕
The ratio of the compound and thionyl chloride to be used is not particularly limited and can be appropriately selected within a wide range, but usually the latter is used in a molar range of 1 to 2 times the former, preferably 1 to 1.2 times the molar amount. Good. The reaction between the compound of formula [] and thionyl chloride is preferably carried out in the presence of a basic compound. Examples of the basic compound used include tertiary amines such as triethylamine, tributylamine, dimethylaniline, diethylaniline, and ethylmorpholine, and pyridine. The amount of such a basic compound to be used is sufficient as long as it can capture the hydrogen chloride produced as a by-product from the above reaction, but it is usually about 1 to 2 times the mole of the compound of formula [],
It is preferable to use 1 to 1.5 times the molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but usually -20°C to 50°C, preferably -10°C to
Performed at 30°C. The reaction time is about 1 to 3 hours. Representative compounds of the present invention thus obtained are listed below. (N-diethylphosphonomethyl-N-cyanomethyl)aminosulfinyl chloride (N-diethylphosphonomethyl-N-ethoxycarbonylmethyl)aminosulfinyl chloride (N-diethylphosphonomethyl-N-butoxycarbonylmethyl) Aminosulfinyl chloride (N-dimethylphosphonomethyl-N-methoxycarbonylmethyl)Aminosulfinyl chloride (N-diphenylphosphonomethyl-N-cyanomethyl)Aminosulfinyl chloride (N-diphenylphosphonomethyl -N-ethoxycarbonylmethyl)aminosulfinyl chloride What should be noted here is that when dialkylaminosulfinyl chloride is produced from a general dialkylamine as a raw material, this compound is unstable and cannot be used as an intermediate. . However, the compound of the present invention is quite stable and can be used as an intermediate for insecticides and herbicides. For example, the production of sulfinyl chloride of dibutylamine cannot be confirmed, but the compound of the present invention can be confirmed, and since the compound of the present invention also reacts with phenols in good yield, the compound of the present invention and phenol are reacted,
By isolating and purifying the reaction product and confirming the product, it can be confirmed that the compound of the present invention is produced as a reaction intermediate. The compound of the present invention can be purified by commonly known means such as extraction, concentration, distillation, column chromatography, and recrystallization. The present invention will be explained in more detail with reference to Examples below. Example 1 Synthesis of (N-diphenylphosphonomethyl-N-cyanomethyl)aminosulfinyl chloride N-
Diphenylphosphonomethyl-N-cyanomethylamine 6g (0.02mol), triethylamine 2.2g
(0.022 mol) and tetrahydrofuran (50 ml) was cooled to -10°C, and 2.4 g (0.02 mol) of thionyl chloride was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the precipitated crystals were filtered. The crystals were washed with 10 ml of tetrahydrofuran, and the mother liquor and the washings were combined and concentrated under reduced pressure at below 30°C to obtain an oil. The NMR (δ, ppm) of the obtained oil in deuterated chloroform was as follows. 4.01 (d, 2H) 4.61 (s, 2H) 7.25 (10H) To further confirm that this oil is the compound of the present invention, the oil was dissolved again in 50 ml of chloroform, and 1.9 g of phenol ( 0.02 mol) was added dropwise, and then 2.2 g (0.022 mol) of triethylamine was added dropwise.
was dripped. After the dropwise addition, the mixture was stirred at room temperature for 5 hours, water was added, and the chloroform layer was separated. The chloroform layer was dried and concentrated to obtain an oil. This oil was purified by silica gel column chromatography (solvent: benzene:ethyl acetate = 4:1) to obtain an oil. NMR of this oil in deuterated chloroform
(δ, ppm) was as follows. 3.94 (dd, 2H) 4.35 (d, 2H) 7.04 (15H) Elemental analysis value (as C ₂₁ H ₁₉ N ₂ O ₅ PS) Analysis value (%) C57.14 H4.29 N6.19 Calculated value (%) C57.01 H4.33 N6.33 From the above results, it was confirmed that it was (N-diphenylphosphonomethyl-N-cyanomethyl)phenoxysulfinamide, thereby confirming the production of the compound of the present invention. Examples 2 to 4 The same operations as in Example 1 were performed to obtain the compounds listed in Table 1 below. Physical properties and NMR in deuterated chloroform are shown. 【table】

Claims (1)

[Claims] 1. General formula A phosphonomethylaminosulfinyl chloride derivative represented by (R ₁ and R ₂ represent alkyl or phenyl; R ₃ represents cyanomethyl or alkoxycarbonylmethyl). 2 General formula (R ₁ and R ₂ represent alkyl or phenyl. R ₃ represents cyanomethyl or alkoxycarbonylmethyl) A general formula characterized by reacting a phosphonomethylamino derivative represented by the following with thionyl chloride. (R ₁ , R ₂ and R ₃ are the same as above) A method for producing a phosphonomethylaminosulfinyl chloride derivative.