JPS601194A - Preparation of o,o-dialkyl s-(acetyl n-alkylcarbamic acid alkylester)-dithiophosphoric ester - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an agricultural chemical in high yield in high quality, by reacting an aqueous solution of an O,O-dialkyldithiophosphate with a solution of an N-haloacetyl N-alkylcarbamic acid alkyl ester in an organic solvent in the presence of a specific catalyst. CONSTITUTION:Preferably 50wt% aqueous solution of an O,O-dialkyldithiophosphate shown by the formula I (M IS alkali metal atom, ammonium; R is 1-4C alkyl) is reacted with a solution of an N-haloacetyl N-alkylcarbamic acid alkyl ester shown by the formula II (X is halogen; R<1> and R<2> are 1-4C alkyl) in an organic solvent (e.g., preferably 50wt% solution in benzene, toluene, etc.) in the presence of one or more catalysts selected from an onium compound, a compound capable of forming an onium compound, and a lactam shown by the formula III (R<3> is H, or 1-5C alkyl; n is 1-5).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteolinic acid ester, and the object thereof is to produce 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteophosphate in high yield. An object of the present invention is to provide a method for producing 0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteolinic acid ester.

0.0-Dialkyl S-(acetyl N-alkylcarbamate alkyl 9-diteolinic acid ester itself and its use as a pesticide (insecticidal diarrhea) are known. A method for preparing N-haloacetyl N-alkylcarbamates from alkyl salts is also known from British Patent No. 867.780.Although this method is an excellent method, it has the disadvantage that 0,0-dialkyl It is necessary to isolate dithiophosphoric acid or its salts, which is not economical in terms of operation, and especially when using the salts, many operations are required before concentration, crystallization, filtration, and drying, making it difficult for industrial use. Furthermore, there is a problem in that the quality of the target product, 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteophosphate, is unknown.

Therefore, the present inventors investigated various methods for producing 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate, and found that using an aqueous solution of 0,0-dialkyl ditheophosphate, N - Haloacetyl N-alkyl carbamate Alkyl 0,0-dialkyl S with high yield and low quality by adopting three configurations: using an organic solvent solution and reacting both in the presence of a specific catalyst. -(acetyl N-
The present invention was completed by discovering that it is possible to industrially produce an alkyl carbamate (alkyl)-diteolin acid ester.

That is, the present invention provides 0,0-dialkyl ditheophosphate and N-
0 from alkyl haloacetyl N-alkylcarbamate
In the method for producing 1o-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteolinic acid ester, the general formula % formula % (1) ) (where M is an alkali metal 1M group or an ammonium group,
R represents a C1-4 alkyl group. ) 0, O-dialkyl dithiophosphate aqueous solution and general formula (]
) (wherein X is a halogen atom, R1 and R2 are the same or different alkyl groups of 01 to 4). Compounds capable of forming general formula (1) % formula % (wherein R3 is a hydrogen atom or an alkyl group of 01 to ., n
represents a positive integer from 1 to 5. ) Production of 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteolinate, characterized by reacting in the presence of one or more catalysts selected from lactams represented by It's a method.

Here 0. As an aqueous solution of O-dialkyl dithiophosphate, phosphorus pentasulfide and alcohol are mixed without solvent or with a hydrocarbon solvent or "/2 P285 + 2ROH→(RO)2PS,!" by a conventional method.
(2S (in the formula, R indicates the above meaning) is the corresponding 0,0-dialkyl ditheolinic acid itself.

The O, o-dialkyl ditheolinic acid obtained by reacting in
M indicates the above meaning. ) During this neutralization reaction, 0. Two layers, an O-dialkyl dithiophosphate aqueous solution layer and an organic layer, are separated, and O1O is added to the organic layer.
- The unequal ester components in the dialkyldithiophosphoric acid are transferred and a highly purified 0.0-dialkyldithiophosphate aqueous solution is obtained, which is also one of the reasons why the target product is obtained with high purity.

Note that the concentration of the 0,0-dialkyl ditheorinate aqueous solution is fine as long as it is below its solubility;
Although it varies depending on the type of 9O-dialkyl ditheorinate, it is usually about 40 to 70% by weight, preferably 50% by weight.
Use the one before and after.

If it is extremely concentrated, it may cause precipitation, and if it is too dilute, it will be difficult to operate the reaction.

Next, the alkyl N-heroacetyl N-alkylcarbamate used in the present invention is usually obtained by the reaction of an alkyl N-alkyl carbamate and a monohaloacetyl halide OOO 1R1 R"ocNHR' + XCCH,X - + XCj
H,ON <C,OOR' +.

(In the formula, R', R''; If it is insufficient, it will react with 0゜0-dialkyl ditheorinate, liberate o-dialkyl ditheoric acid, and complete the reaction between alkyl N-haloacetyl N-alkylcarbamate and 0IO-dialkyl ditheorinate. Taking into consideration that it may inhibit the use of 7-tuberoacetyl halide and contain unreacted products, decomposed products, etc. of the used 7-tuberoacetyl halide, the unreacted 7-tuberoacetyl halide was purified by washing with an organic solvent and water. It is preferable that the alkyl N-haloacetyl N-alkylcarbamate is separated and obtained as a solution in an organic solvent, and the alkyl N-haloacetyl N-alkylcarbamate is separated and obtained as it is for reaction with an aqueous solution of 0.O-dialkyl ditheorinate. Thus purified N-haloacetyl N-
The use of a solution of an alkyl alkyl carbamate in an organic solvent 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. The concentration of the organic solvent solution of the alkyl N-haloacetyl N-alkylcarbamate may be any solution as long as it is below its solubility, and is usually 40 to 70% by weight, although it varies depending on the type of N-haloacetyl N-alkylcarbamate. %
The amount used is preferably around 50% by weight.

If it is extremely concentrated, it may cause precipitation, and if it is too dilute, it will be difficult to operate the reaction.

Further, to explain 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 among them, ammonium compounds, phosphonium compounds, pyridinium compounds,
Arzonium compounds, stibonium compounds, oxonium compounds, sulfonium compounds, selenonium compounds,
Examples include onium compounds such as stibonium compounds and iodonium compounds, compounds that can react with raw materials to form onium compounds when added to the reaction system, and one or more lactams represented by the above general formula (I). can. Specifically, the phosphonium compound has the general formula,
(IV) Examples of ammonium compounds include compounds of general formula (V) and pyridinium compounds of general formula (Vl). (IY), (V)'.

In the formula (vl), R', R5; unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, hydrogen atom,
N-acetyl N-alkylcarbamate alkyl group, A represents a halogen atom, cyano group, inorganic acid or organic acid residue, R8 is a C1-2o substituted or unsubstituted alkyl group, substituted or unsubstituted represents an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, Ro represents a hydrogen atom, an alkyl group of 01 to 4, and m represents 1 to 3. represents a positive integer, and X represents a halogen atom.

More specific phosphonium compounds include triethylbenzylphosphonium chloride, triethyldodecylphosphonium chlorite, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium iodite, and tri-n-butylphosphonium chloride. Butylmethylphosphonium iodite,
tri-n-butylallylphosphonium bromide, tri-n-butylbenzylphosphonium chloride, tetra-n-butylphosphonium 01O-diethylphosphoroditheoate, tri-n-butylhexadecylphosphonium bromide, tri-n-octeleetherphosphonium p40mite , tris-2-cyanoethylallylphosphonium flora (l', triphenylethylphosphonium iotite, triphenylbutylphosphonium bromide, triphenylmethylphosphonium chloride, tetranoenylphosphonium bromide, trisparatrilyethylphosphonium bromide, tribenzylpropylphosphonium) There are iodide, tricyclohexylethylphosphonium iodide, tetrakishydroxymethylphosphonium chloride, bis(tetrakishydroxymethylphosphonium) sulfate, etc.Ammonium compounds include tetramethylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium hydrodiene. Sulfate, trioctylmethylammonium chloride, benzyltrimethylammonium chloride, benlz+z)!
I Etherammonium chloride, benzyltributylammonium chloride, benzyltrimethylammonium fluoride, hexadecyltriethylammonium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dibutyldimethylammonium chloride, decyltriethylammonium bromide, hexyltriethylammonium bromide, F Decyltriethylammonium promite, methyltrinonylammonium chloride, methyltriphenylammonium proma(l'
, octyltriethylammonium bromide, tetrabutylammonium cyanide, tetrabutylammonium iodite, tricaprylmethylammonium chloride, etc., and examples of pyridinium compounds include N-methylpyridinium halide, N-ethelpyridinium halide, and N-pterpyridinium. No1lide, N-laurylpyridinium chloride, N-myristylpyridinium chloride, N-ceylpyridinium halide, N
-stearylpyridinium chloride, N-benzylpyridinium chloride, N-(parachlorobenzyl)pyridinium chloride, N-(valalaurylbenzyl)
Pyridinium chloride, N-hydroxyethylpyridinium chloride, N-carboxymethylpyridinium chloride, N-carbamoylethylpyridinium chloride, N-hydroxyethoxyethylpyridinium chloride, N-allylpyridinium chloride and each 01-4 alkyl group-substituted pyridinium halide,
N-benzyl-(3°5-lutedinium) chloride,
N-lauryl-C3,5-lutedinium) 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-()lycyanoethyl)-picolinium]-iodite, N-benzyl-(4-stilbazolium) chloride, and the like.

In addition, as a compound that can react with the raw material 0.0-dialkyl dithiophosphate or N-haloacetyl N-alkyl tribamine/argyl acid when added to the reaction system to form an onium compound, the general formula (tv)' Phosphine R5 ■ (IV)'R'-P-R1' and general formula (■)' Pyridine (IV)', (V)', (Vl)' In the formula, '
R', 'R', 'R', R'.

m each indicates the above meaning.

Specific examples of lactams include β-propiolactam, γ
-bunarolactam (2-pyrrolidone), γ-valerolactam, δ-no(leroractam (2-piperidone), ε-
Examples include caprolactam, heptolactam, 5-ethel-2-pyrrolidone, 5-ethel-2-biperidone, 5-n-propyl-2-pyrrolidone, and 5-1-butyl-2-piperidone.

The present invention uses the above raw materials to produce the desired product according to the following formula.

Here, there is no problem in dropping either the 0,0-dialkyl ditheorinate aqueous solution or the N-710 acetyl N-alkylcarbamine, and the reaction temperature is 20 to 90°C, preferably 50 to 60°C. React with. If the temperature is less than 20℃, the reaction rate is not sufficient;
It is preferable to avoid high temperatures exceeding 100 mL to prevent decomposition of raw materials and target materials.

The reaction time varies depending on the raw materials, target object, catalyst, reaction temperature, etc., but usually 30 minutes to 10 hours, preferably 3 to 5 hours is sufficient.

In addition, no special consideration is required regarding the manner in which the catalyst is added, and O
, O-dialkyl ditheorinate aqueous solution and N-haloacetyl N-furkylcarnocuminate alkyl organic solvent solution in the reaction system. In this case, the amount present is within the range of 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of 0,0-dialkyl S-(acetyl N-alkylcarbamate alkyl)-dithiophosphate. 0 parts by weight is sufficient, but extremely small amounts have no catalytic activity, and amounts exceeding 10 parts by weight are economically wasteful.

Furthermore, the reaction ratio between 0,0-dialkyl ditheorinate and N-10 acetyl N-alkylcarbamate is usually sufficient in the theoretical amount, but after the reaction is completed, the target product is in the organic solvent layer. Therefore, it is practical to use an excess of 0,0-dialkyl dithiophosphate in order to avoid contamination by unreacted raw materials. In other words, it is recommended to use 0,O-dialkyl dithiophosphate in an amount of 1 to 12 mol per 1 mol of alkyl N-haloacetyl N-alkylcarnocuminate to completely consume the raw material on the organic solvent layer side. preferable.

After the reaction is complete, the target product is extracted into the organic solvent layer, and unreacted O
, ○-dialkyl dithiophosphate, by-product salts, and other impurities are separated from the aqueous solution layer, and then the organic solvent layer is washed and dehydrated according to a conventional method, and the organic solvent is recovered. Target O,O-dialkyl S
-(Alkyl acetyl N-alkylcarbamate)-diteolinic acid 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.

Thus, according to the present invention, since an aqueous solution of 0,O-dialkyl ditheorinate can be used, there is no need for many operations such as concentration, crystallization, filtration, and drying to isolate the salt itself. Moreover, during the production of the salt, impurities from the production of 0,○-dialkyldithiophosphoric acid are removed from the aqueous solution as an oil, resulting in a high-quality target product. Also, one of the raw materials, N
-Haloacetyl N-alkyl Alkyl carbamate can also be used in the form of a solution in an organic solvent, so a purified product can be used, which is useful for obtaining a target product of cylinder quality, and the reaction operation is easy.

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 0,0-diethyl S-(N-ethoxycarbonyl N-
Production of methylcarbamoylmethyl)phosphorodithioate.

0,0-Diethyldithiophosphate aqueous solution (concentration 50
% by weight) 4.5.81 y-(0.11 mol) with catalyst benzyltriethylammonium chloride 0.66F
was added, maintaining the temperature at 55-60°C, and adding Niethyl N under stirring.
-Chloroacetyl N-methylcarbame) 17.96y
A toluene solution of -(0.10 mol) was added dropwise.

After the dropwise addition, the reaction was continued for an additional 6 hours at 60°C with vigorous stirring. After the reaction is complete, the toluene layer is separated, washed with dilute alkaline solution and then water, and the toluene is distilled off under reduced pressure to obtain the target product 0.0-diethyl 5-(N
-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate 32.61y- (yield 99%)
, a purity of 98.5% was obtained.

Note that the purity is the result of measurement by an internal standard method of gas chromatography, and the same applies to other Examples and Comparative Examples.

Example 2 Preparation of O20-diethyl 5-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphorodithioate using various catalysts.

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.

Comparative example ○, O-diethyl 5-(N-ethoxycarbonyl N-
Production of methylcarbamoylmethyl) phosphorodithioate When produced in the same manner as in Example 1 without using a catalyst, the target product 0,0-diethyl 5-(N-ethoxycarbonyl N-methylcarbamoylmethyl)phosphoro Only 25.699 dithioate (yield 78%) and 88% purity were obtained.

Example 3 0,0-dialkyl 5-(N-ethoxycarbonino I
/, N-methylcarbamoylmethyl) phosphorodithioate Production was carried out in the same manner as in Example 1 using 0.11 mol of various sodium dialkyl ditheorinate aqueous solutions (concentration 50% by weight) and using various catalysts shown in Table 2. , ethyl N-chloroacetyl N-methylcarbamate in a toluene solution of 01 mol was reacted. Table 2 shows the yield and purity of the target product obtained as a result.

Example 4 0. O-diethyl 5-(N-alkoxycarbonyl N
- Preparation of (furkylcarbamoyl) phosphorodithioate.

In the same manner as in Example 1, using 0.11 mol of an aqueous solution of sodium 02O-diethylditheophosphate and 1 part by volume of various catalysts per 100 parts by volume of the target product, various alkyl N-chloroacetyls shown in Table 3 below were prepared. N-alkyl carbamate 01
Table 3 shows the yield and purity of each TΦ target product obtained by reacting moles.

Claims (1)

[Claims] i) Production of 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteorinate from o,o-dialkyl ditheorinate and alkyl N-haloacetyl N-alkylcarbamate In the method of formula (1) (% formula %) (in the formula, M represents an alkali metal atom or an ammonium group, and R represents a C1-4 alkyl group) 0.0-dialkyl ditheophosphate aqueous solution and general Formula (n
) (in the formula, X is a halogen atom, R1 and R2 are the same or different alkyl groups of 01 to 4). and one or two lactams selected from compounds capable of forming a compound and a lactam represented by the general formula (1) (wherein R3 is a hydrogen atom or a C3~ alkyl group, and n is a positive integer of 1 to 5). 0 characterized in that the reaction is carried out in the presence of more than one species of catalyst.
, 0-dialkyl S-(acetyl N-alkylcal/<
A method for producing a (alkyl mate)-diteophosphate ester. 2) As onium compounds, phosphonium compounds of general formula (IV), ammonium compounds of general formula (V), and pyridinium compounds (Vl) of general formula (Vl) (in the formula, R'+ R5+ R6, R' are the same or different, respectively) ) C, ~2o substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted cycloalkyl group, hydrogen atom, N-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 substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group. It represents a substituted cycloalkyl group, a substituted or unsubstituted aralkyl group, R9 is a hydrogen atom, 0
It represents an alkyl group of 1 to 4, m represents a positive integer of 1 to 3, and X represents a halogen atom. ) as a compound capable of forming an onium compound, 5 (V)' I R' -N -R' of the general formula (■)' and pyridine of the general formula (■)' 0.0-dialkyl S according to claim 1, wherein R', R5, R', R", and m each have the above meanings. (Alkyl acetyl N-alkylcarbamate)
- A method for producing a dithiophosphoric acid ester. 3) A patent claim in which the catalyst is present in an amount within the range of 0.01 to XOZ parts per 100 parts by weight of the target 0,0-dialkyl S-(acetyl N-alkylcarbamate)-diteophosphate ester. A method for producing 0.0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate according to item 1 or 2. 4) Claims 1 to 3 in which 0.0-dialkyl ditheorinate is reacted in an amount within the range of 1 to 1.2 mol per 1 mol of alkyl N-haloacetyl N-alkylcarbamate. A method for producing a 0,0-dialkyl S-(alkyl acetyl N-alkylcarbamate)-dithiophosphate ester according to any one of the above. 5) Any one of claims 1 to 4 in which an aqueous O20-dialkyl ditheorinate solution and an alkyl N-haloacetyl N-alkylcarbamate organic solvent solution are reacted at a temperature within the range of 20 to 90°C. or 0 described in item 1
A method for producing 1O-dialkyl S-(alkyl acetyl N-alkylcarbamate)-diteolinic acid ester.