JPH0225916B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides O,O-dialkyl S-(acetyl N
The purpose of this method is to produce O,O-dialkyl S-(acetyl N-alkyl carbamate)-dithiophosphate in high yield and high quality. An object of the present invention is to provide a manufacturing method. O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphates themselves and their use as agricultural chemicals (insecticides) are known. A method for producing it from O,O-dialkyl dithiophosphoric acid or a salt thereof and an alkyl N-haloacetyl N-alkyl carbamate is also known from British Patent No. 867,780. Although this method is an excellent method, it is not economical in terms of operation because it requires the isolation of O,O-dialkyl dithiophosphoric acid or its salt, and especially when the salt is used, it is concentrated for isolation. , requiring many operations such as crystallization, filtration, and drying, and is not industrially practical. Furthermore, there is a problem in that the quality of the target O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate ester is unknown. Therefore, the present inventors proposed O,O-dialkyl S-
(alkyl acetyl N-alkylcarbamate)-
As a result of various studies on methods for producing dithiophosphate esters, we found that using an aqueous O,O-dialkyl dithiophosphate solution, using an alkyl N-haloacetyl N-alkyl carbamate organic solvent solution, and using both in the presence of a specific catalyst. We have discovered that it is possible to industrially produce high-yield, high-quality O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate esters by employing three configurations: The invention has been completed. That is, the present invention provides a method for producing O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate from an O,O-dialkyldithiophosphate and an alkyl N-haloacetyl N-alkylcarbamate, which generally It is expressed by the formula (). (In the formula, M represents an alkali metal atom or an ammonium group, and R represents a _C1-4 alkyl group.) An aqueous solution of O,O-dialkyl dithiophosphate is represented by the general formula (). (In the formula, X represents a halogen atom, and R ¹ and R ² represent the same or different C _{1 to 4} alkyl groups.) N-haloacetyl N-alkyl carbamate is combined with an organic solvent solution to form an onium compound. Possible compounds and general formulas () (In the formula, R ³ is a hydrogen atom or a C _1-5 alkyl group,
n represents a positive integer of 1 to 5. ) A method for producing O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphoric acid ester, which comprises reacting in the presence of one or more catalysts selected from lactams represented by It is. Here, as the O,O-dialkyl dithiophosphate aqueous solution, phosphorus pentasulfide and alcohol are prepared in a conventional manner without a solvent or in a hydrocarbon solvent. (In the formula, R indicates the above meaning.) is an alkali metal (Na, K, Li) hydroxide aqueous solution of O, O-dialkyl dithiophosphoric acid obtained by reacting it in the corresponding O, O-dialkyl dithiophosphoric acid itself. Or use one neutralized with ammonia water, etc. (In the formula, R and M have the above meanings.) During this neutralization reaction, two layers, an O,O-dialkyl dithiophosphate aqueous solution layer and an organic layer, are separated,
Impurities in O,O-dialkyl dithiophosphoric acid to the organic layer, e.g.

[Formula] (RO) ₃ PS The ester components such as the like are transferred and a highly pure O,O-dialkyl dithiophosphate aqueous solution is obtained, which is also one of the reasons why the target product can be obtained with high purity. Note that the concentration of the O,O-dialkyldithiophosphate aqueous solution is fine as long as it is below its solubility, and although it varies depending on the type of O,O-dialkyldithiophosphate, it is usually about 40 to 70% by weight. Preferably, the amount is about 50% by weight. If it is extremely concentrated, it may cause precipitation, and if it is too dilute, it is uneconomical in terms of reaction operation. Next, the alkyl N-haloacetyl N-alkylcarbamate used in the present invention is usually a reaction between an alkyl N-alkyl carbamate and a monohaloacetyl halide. (In the formula, R ¹ , R ² , and X have the meanings described above.) The one obtained from the formula is used. This substance is generally crystalline at room temperature and is not easy to handle as it is, and if the removal of by-product HX is insufficient, it will react with O,O-dialkyl dithiophosphate.
O,O-dialkyldithiophosphoric acid is liberated and N-
Considering that it inhibits the completion of the reaction between the alkyl haloacetyl N-alkyl carbamate and the O,O-dialkyl dithiophosphate, and that it contains unreacted products, decomposed products, etc. of the monohaloacetyl halide used, Wash and purify with solvent and water to produce by-products
HX or unreacted monohaloacetyl halide,
The decomposition products are transferred to the aqueous layer, and N-haloacetyl N
It is preferable that the alkyl -alkylcarbamate is separated and obtained as a solution in an organic solvent and subjected to the reaction as it is with an aqueous O,O-dialkyldithiophosphate solution. The use of an organic solvent solution of alkyl N-haloacetyl N-alkylcarbamate purified in this manner is also one of the reasons why a highly purified target product can be obtained. The most suitable organic solvents here include one or more of aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons, and ethers. N-haloacetyl N
-The concentration of the alkyl alkyl carbamate in the organic solvent is fine as long as the solution is below its solubility, and although it varies depending on the type of N-haloacetyl N-alkyl alkyl carbamate, it is usually 40~
About 70% by weight, preferably about 50% by weight is used. If it is extremely concentrated, it may cause precipitation, and if it is too dilute, it is uneconomical in terms of reaction operation. Further explaining the catalyst of the present invention, any so-called phase transfer catalyst used for the reaction between an aqueous solution and an organic solvent solution can be applied, but ammonium compounds, phosphonium compounds, pyridinium compounds, arzonium compounds, and stibonium compounds are particularly applicable. , oxonium compounds,
Onium compounds such as sulfonium compounds, selenonium compounds, stannonium compounds, and iodonium compounds; compounds that can react with raw materials to form onium compounds when added to the reaction system; and one or two types of lactams represented by the above general formula (). The above can be mentioned. Specifically, the phosphonium compound has the general formula ()

Compounds of [formula], ammonium compounds are general formula () formula

Compounds of [formula], pyridinium compounds are general formula () formula The following compounds can be mentioned. (), (),
In the formula (), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different C _{1 to 20} substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkenyl groups, Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a hydrogen atom, an alkyl N-acetyl N-alkylcarbamate group, and A represents a halogen atom, a cyano group, or a residue of an inorganic or organic acid. , R ⁸ is a C _1-20 substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group ^R9 represents a hydrogen atom, _C1-4 alkyl group, m represents a positive integer of 1-3, and X represents a halogen atom. More specifically, the phosphonium compounds include:
Triethylbenzylphosphonium chloride, triethyldodecylphosphonium chloride, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-
n-butylphosphonium iodide, tri-n-
Butylmethylphosphonium iodide, tri-n
-Butylarylphosphonium bromide, tri-
n-Butylbenzylphosphonium chloride, tetra-n-butylphosphonium O,O-diethylphosphorodithioate, tri-n-butylhexadecylphosphonium bromide, tri-n-octylethylphosphonium bromide, tris-2
-cyanoethylallylphosphonium chloride,
Triphenylethylphosphonium iodide, triphenylbutylphosphonium bromide, triphenylmethylphosphonium chloride, tetraphenylphosphonium bromide, trisparatriethylphosphonium bromide, tribenzylpropylphosphonium iodide, tricyclohexylethylphosphonium iodide, tetrakishydroxymethylphosphonium chloride,
Bis(tetrakishydroxymethylphosphonium) sulfate, etc., and ammonium compounds include tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium Chloride, benzyltributylammonium chloride, benzyltrimethylammonium fluoride, hexadecyltriethylammonium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dibutyldimethylammonium chloride, decyltriethylammonium bromide, hexyltriethylammonium bromide, dodecyltriethylammonium bromide , methyltrinonylammonium chloride, methyltriphenylammonium bromide, octyltriethylammonium bromide, tetrabutylammonium cyanide, tetrabutylammonium iodide, tricaprylmethylammonium chloride, etc., and the pyridinium compounds include N-methylpyridinium halide, N-ethylpyridinium halide, N-butylpyridinium halide, N
-Laurylpyridinium chloride, N-myristylpyridinium chloride, N-cecylpyridinium halide, N-stearylpyridinium chloride, N-benzylpyridinium chloride, N-(parachlorobenzyl)pyridinium chloride, N-(paraurylbenzyl)pyridinium chloride, N- -Hydroxyethylpyridinium chloride, N-carboxymethylpyridinium chloride, N-carbamoylethylpyridinium chloride, N-hydroxyethoxyethylpyridinium chloride, N- _{allylpyridinium} chloride and each _C1-4 alkyl group-substituted pyridinium halide, N-benzyl-
(3,5-lutidinium) chloride, N-lauryl-(3,5-lutidinium) chloride, N
-Alkyl-(4-alkylpyridinium) chloride, N-benzyl-(4-alkylpyridinium) chloride, N-alkyl-(4-phenylpropylpyridinium) chloride, N-benzyl-(4-phenylpropylpyridinium) chloride , N,N'-dialkyl-(1,3-dipyridiniumpropane)-dichloride, N,N'-
Dibenzyl-(1,3-dipyridiniumpropane)
-dichloride, N-methyl-[4-(tricyanoethyl)-picolinium]-iodide, N-benzyl-(4-stilbazolium) chloride, and the like. Also, when added to the reaction system, O, O of the raw material
-Dialkyldithiophosphates, or compounds that can react with alkyl N-haloacetyl N-alkylcarbamates to form onium compounds include phosphine of general formula ()'

【formula】 Amine of general formula ()′

Pyridine of [formula] and general formula ()′ can be mentioned. In formulas ()′, ()′, ()′, R ⁴ ,
R ⁵ , R ⁶ , R ⁹ and m each have the above meanings. Specific examples of lactams include β-propiolactam, γ-butyrolactam (2-pyrrolidone),
γ-valerolactam, δ-valerolactam (2-
piberidone), ε-caprolactam, heptolactam, 5-ethyl 2-pyrrolidone, 5-ethyl 2
-piperidone, 5-n-propyl 2-pyrrolidone, 5-i-butyl 2-piperidone, and the like. The present invention uses the above raw materials to produce the desired product according to the following formula. Here, the O,O-dialkyl dithiophosphate aqueous solution and the alkyl N-haloacetyl N-alkylcarbamate organic solvent solution may be mixed, or either one may be added dropwise, and the reaction temperature is 20°C. The reaction is carried out at ~90°C, preferably 50-60°C. The reaction rate is insufficient below 20°C, and high temperatures above 90°C are preferably avoided in order to prevent decomposition of raw materials and target substances. The reaction time varies depending on the raw materials, target substance, catalyst, reaction temperature, etc., but is usually 30 minutes to 10 hours.
Preferably, 3 to 5 hours is sufficient. or,
No special consideration is required regarding the manner in which the catalyst is added;
O,O-dialkyl dithiophosphate aqueous solution and N-
It is sufficient that the alkyl haloacetyl N-alkylcarbamate is present in the reaction system of the alkyl organic solvent solution. Regarding the amount present at that time, the target O,O-dialkyl S-(acetyl N-alkylcarbamate alkyl)-dithiophosphate ester
A range of 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight is sufficient. If it is used in an extremely small amount, it has no catalytic ability, and if it exceeds 10 parts by weight, it is economically wasteful. Moreover, O,O-dialkyl dithiophosphate and N-
The reaction ratio with the alkyl haloacetyl N-alkyl carbamate is usually sufficient in the theoretical amount, but since the target product moves to the organic solvent layer after the reaction is completed, O,
It is practical to use an excess of the O-dialkyl dithiophosphate side. That is, N-haloacetyl N-
It is preferable to use O,O-dialkyl dithiophosphate in an amount within the range of 1 to 1.2 mol per 1 mol of alkyl carbamate so that the raw material on the organic solvent layer side is completely consumed. After the reaction is complete, the target product is extracted into the organic solvent layer,
This is separated from the aqueous solution layer containing unreacted O,O-dialkyl dithiophosphate, by-product salts, and other impurities.Then, the organic solvent layer is washed in a conventional manner, and the organic solvent is recovered after dehydration. By doing so, the target O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate ester can be obtained in high yield and quality. It goes without saying that the recovered organic solvent at this time can be used repeatedly. Since the O,O-dialkyl dithiophosphate aqueous solution according to the present invention can thus be used, it is not necessary to perform many operations such as concentration, crystallization, filtration, and drying in order to isolate the salt itself. During production, impurities from O,O-dialkyldithiophosphoric acid production are removed from the aqueous solution as an oil, resulting in a high quality target product. In addition, one of the raw materials, alkyl N-haloacetyl N-alkylcarbamate, can be used as a solution in an organic solvent, so purified products can be used, which is useful for obtaining high-quality target products, and the reaction operation is easy. can get. Moreover, although it is normally not easy to carry out a reaction in a mixed system between an aqueous solution layer and an organic solvent layer, by using the catalyst of the present invention, it is possible to obtain the desired product, which is currently used as an insecticide, in a high yield close to the theoretical value. The industrial significance of the present invention is extremely large. Hereinafter, the present invention will be explained in more detail with reference to comparative examples and examples. Example 1 Preparation of O,O-diethyl S-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate. Add 0.33 g of benzyltriethylammonium chloride catalyst to 45.81 g (0.11 mol) of O,O-sodium diethyldithiophosphate aqueous solution (concentration 50% by weight), maintain the temperature at 55-60°C, and add ethyl N-
Chloroacetyl N-methyl carbamate 17.96g
(0.10 mol) in toluene was added dropwise. After the dropwise addition, the reaction was continued for 3 hours with vigorous stirring at 60°C. After the reaction, the toluene layer was separated, washed with dilute alkaline solution and then water, and the toluene was distilled off under reduced pressure to obtain the target product O as a yellow liquid. , O-diethyl S-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate (32.61 g (yield 99%), purity 98.5%) was obtained. Note that the purity indicates the result of measurement by the internal standard method of gas chromatography, and the same applies to other Examples and Comparative Examples. Example 2 Using various catalysts, O,O-diethyl S-
Preparation of (N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate. The same operations as in Example 1 were carried out using various catalysts shown in Table 1 below in place of the benzyltriethylammonium chloride catalyst used in Example 1. Table 1 shows the yield and purity of the target product obtained as a result.
It was shown to. Comparative Example Preparation of O,O-diethyl S-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate. When produced in the same manner as in Example 1 without using a catalyst, the target product O,O-diethyl S-(N-
25.69 g of ethoxycarbonyl N-methylcarbamoylmethyl) phosphorodithioate (yield 78
%), with a purity of only 88%.

【table】

Table: Example 3 Preparation of O,O-dialkyl S-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate. In the same manner as in Example 1, ethyl N
A solution of 0.1 mol of -chloroacetyl N-methylcarbamate in toluene was reacted. Table 2 shows the yield and purity of the target product obtained as a result.

【table】

[Table] Example 4 Preparation of O,O-diethyl S-(N-alkoxycarbonyl N-alkylcarbamoyl)phosphorodithioate. In the same manner as in Example 1, using 0.11 mol of O,O-sodium diethyldithiophosphate aqueous solution and 1 part by weight of various catalysts per 100 parts by weight of the target product, the following Table 3 was obtained.
Table 3 shows the yield and purity of the various desired products obtained by reacting 0.1 mol of various alkyl N-chloroacetyl N-alkyl carbamates shown in Table 3.

【table】

Claims (1)

[Claims] 1. Process for producing O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate from O,O-dialkyldithiophosphate and alkyl N-haloacetyl N-alkylcarbamate is expressed by the general formula (). (In the formula, M represents an alkali metal atom or an ammonium group, and R represents a _C1-4 alkyl group.) An aqueous solution of O,O-dialkyl dithiophosphate is represented by the general formula (). (In the formula, X represents a halogen atom, and R ¹ and R ² represent the same or different C _{1 to 4} alkyl groups.) N-haloacetyl N-alkyl carbamate is combined with an organic solvent solution to form an onium compound. Possible compounds and general formulas () (In the formula, R ³ is a hydrogen atom or a C _1-5 alkyl group,
n represents a positive integer of 1 to 5. ) A method for producing O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphoric acid ester, which comprises reacting in the presence of one or more catalysts selected from lactams represented by . 2 As an onium compound, a phosphonium compound of general formula () Ammonium compound of general formula () and pyridinium compounds of general formula () (In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ are the same or different C _{1 to 20} substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, hydrogen atom, N-
Represents an acetyl N-alkylcarbamate alkyl group, A represents a halogen atom, a cyano group, a residue of an inorganic acid or an organic acid, and ^R8 represents a _C1-20 substituted or unsubstituted alkyl group, substituted or unsubstituted represents an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, ^R9 represents a hydrogen atom, a _C1-4 alkyl group, and m represents 1 It represents a positive integer of ~3, and X represents a halogen atom. ) as a compound capable of forming an onium compound, phosphine of the general formula ()' [Formula] amine of the general formula ()' and pyridine of general formula ()' (In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁹ , and m each have the above-mentioned meanings.) A method for producing S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate. 3 O,O-dialkyl S- whose catalyst is the target object
(alkyl acetyl N-alkylcarbamate)-
0.01 to 10 per 100 parts by weight of dithiophosphate ester
O,O-dialkyl S- according to claim 1 or 2, present in an amount within the range of parts by weight.
(alkyl acetyl N-alkylcarbamate)-
Method for producing dithiophosphoric acid ester. 4 Any one of claims 1 to 3 in which O,O-dialkyl dithiophosphate is reacted in an amount within the range of 1 to 1.2 mol per 1 mol of alkyl N-haloacetyl N-alkylcarbamate. O,O-dialkyl S-(acetyl N
-Production method of alkyl carbamate)-dithiophosphate ester. 5. Any one of claims 1 to 4, in which an aqueous O,O-dialkyl dithiophosphate solution and an alkyl N-haloacetyl N-alkylcarbamate organic solvent solution are reacted at a temperature within the range of 20 to 90°C. The method for producing O,O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate according to item 1.