JPH0242838B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an amide thionophosphate, and more specifically, a method for producing a high quality amide thionophosphate in a high yield by reacting an amide thionophosphate halide with a phenol using a specific onium compound as a catalyst. This relates to a manufacturing method. Conventionally, methods for producing amide thionophosphate esters are already known in many documents, but
They are mainly used in the reaction between amide thionophosphate ester halides and phenols, by converting the phenol into a phenol salt and reacting it with the amide thionophosphate halides, or by using an acid such as an alkali metal carbonate, bicarbonate or an organic base. A method of coupling in the presence of a binding agent has been used. However, when using the former phenol salt, for example, when the Na salt of phenol is used, the reaction is carried out in a basic state, so the amidothionophosphate halides are hydrolyzed extremely quickly (J.Chem.Soc. (B) 1968, P539) Moreover, since phenol salts are not soluble in ordinary solvents, a heterogeneous reaction between liquid phase and solid phase occurs, which is not preferable because sufficient reaction does not occur. When using the latter acid binder, for example, Japanese Patent Publication No. 56-5233 discloses a method using γ-picoline as the acid binder, but the reaction temperature is low and the reaction rate is extremely slow. It takes a long time to react, and on the other hand,
No. 36712 discloses a method of carrying out the reaction at high temperature in a short time in the presence of an acid binder, but the amide thionophosphate halides are extremely unstable at high temperatures, so they decompose and the resulting amide thionophosphate It has the disadvantage of low ester quality and low yield. On the other hand, Japanese Patent Publication No. 56-52914 discloses a method for producing amide thionolinate using a fatty acid amide as a solvent, but although this method improves the purity and yield of the product obtained, Fatty acid amides are expensive and have a high boiling point, so it is necessary to recover the solvent and replace it with a water-insoluble solvent in the product washing process after the reaction, and loss of solvent cannot be avoided at this time. There are some industrially disadvantageous drawbacks. The present inventors conducted research in view of the above-mentioned conventional techniques, and found that by reacting amidothionophosphate halides, which are easily decomposed in an alkaline atmosphere, with phenols using a catalyst made of a specific onium compound, The present invention was completed based on the finding that the reaction proceeds rapidly without decomposition of the amide thionophosphate halides, and that high quality amide thionophosphate esters can be obtained in high yields. That is, the present invention has the general formula [In the formula, R ¹ and R ² represent a lower alkyl group, and Hal represents a halogen atom. ] Amidothionophosphate halides represented by the general formula [In the formula, X represents a nitro group, a lower alkyl group, a halogen atom, a lower alkoxyl group, a lower alkylmercapto group, a cyano group, a lower alkoxycarbonyl group, or a hydrogen atom, and n represents an integer of 1 to 5. M
represents a hydrogen atom, an alkali metal atom, or an ammonium group. ] As a catalyst, in the reaction with phenols represented by the general formula A phosphonium compound represented by the general formula Ammonium compound represented by and general formula A pyridinium compound represented by [formula,,
, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁸ are each the same or different C _1-20 substituted or unsubstituted alkyl group, aryl group, alkenyl group, aralkyl group, or cycloalkyl group. , A represents a halogen atom, a cyano group, a residue of an inorganic acid or an organic acid, R ⁷ represents a C _1-4 alkyl group or a hydrogen atom,
m represents an integer of 1 to 3. It is characterized by using one or more selected from the following. general formula [In the formula, R ¹ , R ² , X, and n are the same as above] This is a method for producing an amidothionophosphate ester represented by the following formula. The production method of the present invention is illustrated by the following reaction formula.

【formula】

In the general formula (), R ¹ and R ² specifically represent lower alkyl groups such as methyl, ethyl, n-(or iso-)propyl, n-(iso-, sec-, or tert-)butyl. Specifically, Hal represents a halogen atom such as fluor, chloro, bromo, or iodine, and among the halogen atoms, chlor is preferable. Specific examples of amidothionophosphate halides represented by the general formula () include O-methyl-N-iso-propylamidothionophosphate chloride, O-ethyl-N-iso-propylamidothionophosphate chloride, O-iso
-Propyl-N-iso-propylamide thionophosphate ester chloride, O-methyl-N-sec-
Butylamidothionophosphate ester chloride, O
-ethyl-N-sec-butylamidothionophosphate ester chloride, O-iso-propyl-N-sec
-butylamidothionolinate ester chloride, etc. can be mentioned. On the other hand, specific examples of phenols represented by the general formula () include 2-nitrophenol, 2-
Nitro-4-methylphenol, 2-nitro-5
-methylphenol, 3-methyl-4-nitrophenol, 2-nitro-5-chlorophenol,
2-nitro-4-methoxyphenol, 2-nitro-4-methylmercaptophenol, 4-cyanophenol, 2,4-dichlorophenol, 4
- Phenols such as methoxycarbonylphenol or sodium, potassium,
Examples include alkali metal salts or ammonium salts such as. Furthermore, in the general formula (), M represents a hydrogen atom, an alkali metal atom, an ammonium group, etc. as described above, but when M is a hydrogen atom, it is necessary to carry out the reaction in the presence of an acid binding agent. Examples of such acid binders include commonly used alkali metal carbonates, bicarbonates, hydroxides, alcoholates, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. It is also possible to form salts of the phenol, preferably alkali metal or ammonium salts, without the presence of an acid binder, and then react this salt with the amidothionophosphate halide. The catalyst used in the method of the present invention is a specific onium compound such as a phosphonium compound of the general formula (), an ammonium compound of the general formula (), or a pyridinium compound of the general formula (). In order to prevent the decomposition of other substances, those with low deliquescent properties are preferred. Specific examples of the catalyst include trimethylbenzylphosphonium chloride, triethylbenzylphosphonium bromide, tetrabutylphosphonium bromide,
Tetrabutylphosphonium iodide, tributylmethylphosphonium iodide, tetrabutylphosphonium hydrogen sulfate, tetrabutylphosphonium acetate, tributylbenzylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium bromide, etc., and as an ammonium compound is tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium bromide, tributylbenzylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethyl Examples of the pyridinium compound include ammonium chloride, N-laurylpyridinium chloride, N-laurylpicolinium chloride, and N-benzylpicolinium chloride. The amount of catalyst used is 0.1 to 10% by weight, preferably 1 to 5% by weight based on the target amide thionophosphate.
It is preferable that the amount is less than 0.1% by weight, and there is no effect of promoting the reaction, and more than 10% by weight is not appropriate because there is a strong tendency to cause side reactions. Next, as a solvent, ketones, nitriles, halogenated hydrocarbons, hydrocarbons, etc. can be used, and industrially,
In consideration of cleaning after the reaction, a poorly water-soluble material such as methyl isobutyl ketone (hereinafter referred to as MIBK) is preferable. Next, the manufacturing method of the present invention will be specifically explained.
In the first stage reaction, for example, phenol is first dissolved in a solvent, and an acid binder and a catalyst are added. Then, phenol salts are formed and heat is generated. In this case, it is preferable to heat and ripen. The liquid temperature at that time is preferably above normal temperature and below the boiling point of the solvent. The catalyst may be added at the next stage of the reaction, but
It is more effective if added from the beginning. Alternatively, as another example, a phenol salt may be suspended in a solvent together with a catalyst. As a second step reaction, an amidothionophosphate ester can be synthesized by dropping the amidothionophosphate halides into a solvent in which the above-mentioned phenol salt and catalyst are suspended while stirring. In this reaction, the reaction temperature is 10~
110℃, preferably 20~70℃ is suitable, 10℃
If the temperature is below 110°C, the reaction will not proceed, and if the temperature exceeds 110°C, the raw material, amide thionophosphate halide, will decompose, resulting in a decrease in both yield and quality. A reaction time of 0.5 to 10 hours, usually 1 to 6 hours is sufficient. The details of the mechanism of action of the catalyst in the present invention are unknown, but since the catalyst used belongs to a so-called phase transfer catalyst, it is presumed that a common mechanism of action is operating between the liquid phase and the solid phase. Ru. The amide thionophosphate halide used as a raw material in the present invention is unstable, and the pyroform is formed not only in the presence of water in the reaction system but also in the absence of water.

[Formula] is likely to occur, but by using a catalyst as in the present invention, the coupling reaction proceeds faster than decomposition, so the reaction is completed in a short time at a low temperature, and the desired amide thionophosphate ester can be obtained with a purity of 87 to 97. High quality, true yield of 85~97%
It can be obtained with a high yield of %. In addition, when MIBK, which is poorly soluble in water, is used as a solvent, it is possible to wash and purify it by adding water immediately after the reaction, and MIBK is a low-cost solvent that is commonly used industrially. , dehydration is required when reusing the solvent, but using MIBK is advantageous because dehydration can be easily performed. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 and Comparative Example 1 153 g of 2-nitro-4-methylphenol (1
mol) in 700 ml of MIBK. 138g (1 mol) of potassium carbonate is finely ground while stirring the liquid.
Add. Then, 9 g of tetrabutylammonium bromide was added as a catalyst, and the mixture was aged at 50°C for 2 hours. While stirring this suspension vigorously, 206
g (1.1 mol) of O-methyl-N-iso-propylamidothionophosphate ester chloride are added dropwise at 40°C. After aging at the same temperature for 1.5 hours, it is cooled to room temperature, washed with water to remove inorganic salts, and further washed with a dilute aqueous alkaline solution and water. Then, when MIBK was recovered under reduced pressure, a yellow solid, O-
308 g of (2-nitro-4-methylphenyl)-O-methyl-N-iso-propylphosphoramide thioate were obtained. Analysis by gas chromatography showed that the purity was 90%. This is the true yield
This corresponds to 91%. (Comparative Example 1) The yield was 62% when the same procedure as in Example 1 was performed without adding a catalyst. (Known Example) The yield is 60% according to the same method as in Japanese Patent Publication No. 49-36712. The following can be seen from the above results. Conventionally, O-
The yield of (2-nitro-4-methylphenyl)-O-methyl-N-iso-propylphosphoramidothioate was extremely low. Using the same method as in Japanese Patent Publication No. 49-36712, the yield is 60%, but this is because the raw material O-methyl-N-iso-propylamidothionophosphate chloride is extremely unstable and decomposes during the reaction. This is because you end up doing it. According to the present invention, the reaction proceeds at a low temperature (40°C) and in a short time (1.5 hours), and a product with a yield of 91% and a purity of 90% can be obtained. In this case, without catalyst, the yield is 62
%. Moreover, in this case, even if the temperature is increased for a long time, the yield will not improve. Example 2 Catalyst tetrabutylphosphonium bromide 7g
After dissolving in 700 ml of acetonitrile, 175 g of sodium salt of 2-nitro-4-methylphenol
(1 mol) and stir vigorously. Then O-
Methyl-N-iso-propylamidothionolinate chloride is added dropwise at 30°C. After aging at the same temperature for 5 hours, it was cooled to room temperature. Pour the reaction solution into 800ml of ice water. The precipitate is extracted with 800 ml of toluene and washed with dilute alkaline solution and water.
Next, when toluene was recovered under reduced pressure, O-(2-nitro-4-methylphenyl)-O-methyl-N-iso
311 g of -propyl phosphoroamide thioate were obtained. According to gas chromatography analysis, the purity was 88%. This corresponds to a true yield of 90%. Examples 3 to 8 Examples 3 to 8 were operated in exactly the same manner as in Example 1, using various catalysts shown in Table 1 in place of tetrabutylammonium bromide. The results are also shown in Table 1.

[Table] Example 9 2-nitro-5-methylphenol 153g (1
mol) in 700 ml of MIBK. 138g of potassium carbonate is finely ground while stirring the liquid vigorously.
(1 mol) is added. Then, 12 g of tributylmethylphosphonium iodide was added as a catalyst.
Matured at 50℃ for 1 hour. Next, under vigorous stirring at 40°C, 215 g (1 mol) of O-ethyl-N-sec-butylamidothionophosphate chloride was added.
It was added dropwise and further aged for 3 hours at the same temperature. Cool to room temperature and wash with water to remove inorganic salts, and then wash with dilute aqueous alkaline solution and water. Then, when MIBK was recovered under reduced pressure, a yellowish brown oily substance O-(2-nitro-5-methylphenyl)-
329 g of O-ethyl-N-sec-butyl phosphoramidothioate was obtained. Analysis by gas chromatography showed that the purity was 97%. This corresponds to a true yield of 96%. (Publicly known example) Japanese Patent Publication No. 16854 (1972)
According to the method similar to No. 36342), the yield is 72%. Examples 10 to 12 The same procedure as in Example 9 was carried out except that various catalysts shown in Table 2 were used in place of tributylmethylphosphonium iodide. The results are also shown in Table 2.

[Table] Example 13 2-nitro-5-chlorophenol 174g (1
mol) in 700 ml of MIBK. 138g of potassium carbonate is finely ground while stirring the liquid vigorously.
(1 mol) is added. Then, 7 g of tetrabutylphosphonium iodide was added as a catalyst, and the mixture was aged at 80°C for 1.5 hours. Next, 215 g (1 mol) of O-ethyl-N-sec-butylamidothionophosphate chloride was added dropwise to the mixture under vigorous stirring at 45 DEG C., and the mixture was further aged at the same temperature for 3 hours. After cooling to room temperature, the mixture is washed with water to remove inorganic salts, and further washed with a dilute aqueous alkaline solution and water. MIBK was then recovered under reduced pressure, and a yellow oil, O-(2-nitro-5-chlorophenyl)-O-
349 g of ethyl-N-sec-butyl phosphoroamide thioate were obtained. According to gas chromatography analysis, the purity was 96%. This corresponds to a true yield of 95%.

Claims (1)

[Claims] 1 General formula [Formula] [In the formula, R ¹ and R ² represent a lower alkyl group, and Hal represents a halogen atom. ] Amidothionolinate halides represented by the general formula [Formula] [where X is a nitro group, a lower alkyl group, a halogen atom, a lower alkoxyl group, a lower alkylmercapto group, a cyano group, a lower alkoxycarbonyl group, or a hydrogen atom] , n represents an integer of 1 to 5. M
represents a hydrogen atom, an alkali metal atom, or an ammonium group. ] In the reaction with phenols represented by formula, a phosphonium compound of the general formula [formula], an ammonium compound of the general formula [formula] and a pyridinium compound of the general formula [formula] [in the formula, ,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ are each the same or different C _1-20 substituted or unsubstituted alkyl group,
Represents an aryl group, alkenyl group, aralkyl group, or cycloalkyl group, A represents a halogen atom, a cyano group, a residue of an inorganic acid or an organic acid, and R ⁷ represents C _1-4
represents an alkyl group or a hydrogen atom, and m represents an integer of 1 to 3. ) A method for producing an amidothionophosphate ester represented by the general formula [Formula] [wherein R ¹ , R ² , X, and n are the same as above], characterized by using one or more selected from the following.