JPS6143359B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing thiophosphoric acid derivatives. Therefore, the present invention has the formula: [In the formula, R ₁ is C ₁ to C ₅ alkyl, X is hydrogen,
Represents chlorine or bromine. ] A compound represented by the formula: [In the formula, Y ₁ represents C ₁ to C ₅ alkoxy, chlorine or bromine, Y ₂ represents chlorine or bromine, and Y ₃ represents chlorine or bromine. ] is characterized by condensing the compound represented by the formula: [In the formula, R ₁ , X, Y ₁ and Y ₂ have the same meanings as above, -
CH ₃ and -COOR ₁ group are crotonic acid moieties, one in cis position relative to the other. ] The present invention provides a method for producing a compound represented by the following. Suitable phase transfer catalysts are quaternary ammonium and quaternary phosphonium compounds and crown ethers. Preferred are quaternary ammonium and quaternary phosphonium compounds. A preferred quaternary ammonium salt is tetra(C ₁
~ _C20 ) alkyl and benzyl tri( _C1 ~ _C20 )
Alkylammonium salts, such as sulfates, phosphates, benzenesulfonates, toluenesulfonates and especially hydrohalides such as chlorides, bromides and iodides. Detailed examples of quaternary ammonium salts are benzyltrimethylammonium bromide and hydroxide, benzyltriethylammonium bromide and chloride, benzyltributylammonium bromide, cetyltrimethylammonium bromide, methyltributylammonium chloride, bromide, Tetraethylammonium iodide and hydroxide, tricaprylmethylammonium chloride, Centrimide™ and tetrabutylammonium chloride, bromide, iodide, hydrogen sulfate and hydroxide. Preferred quaternary phosphonium salts are tetraphenyl, triphenyl( _C1 - _C20 ) alkyl and tetra( _C1 - _C20 )alkyl phosphonium salts such as halide salts. Specific examples of quaternary phosphonium salts are benzyltriphenylphosphonium chloride and tetraphenylphosphonium bromide and chloride. Examples of crown ethers are 18-crown-6, 15
-Crown-5 and 12-Crown-4. Preferred alkalis are sodium or potassium hydroxide, especially 10-30% by weight when present in the aqueous phase
In particular 15-25% by weight. The organic phase consists of any suitable inert water-immiscible solvent such as halogenated hydrocarbons such as o-dichlorobenzene, methylene dichloride, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene and chloroform. The reaction is preferably carried out at -10 to +25°C, especially -5 to +5°C. This method enables stereospecific synthesis of compound [] in high yield and high purity. The compound [] has the formula: [In the formula, R ₁ and X have the same meanings as above, R ₂ is C _1
-C5 alkyl, _R3 represents _C1 - _C5 alkyl, _-CH3 and _-COOR1 groups are crotonic acid moieties, one in cis position relative to the other. ] This is a known intermediate useful in the production of the compound shown below. Compound [] is a formula: [In the formula, R ₁ , X, R ₂ and Y ₂ have the same meanings as above, and -CH ₃ and -COOR ₁ groups are crotonic acid moieties, and one is in the cis position relative to the other. ] A compound represented by the formula: R ₃ NH ₂ [] [In the formula, R ₃ has the same meaning as above. ] or condensed with a compound represented by b formula: [In the formula, Y ₂ , X and R ₁ have the same meanings as above, Y' ₁
represents chlorine or bromine, and the _-CH3 and _-COOR groups are crotonic acid moieties, one in the cis position relative to the other. ] A compound represented by the formula: R ₂ OM [ ] [wherein R ₂ has the same meaning as above, and M represents hydrogen, an alkali metal, or an ammonium cation. ] Compound [1a] is produced by condensation with the compound shown below, and then the above method a is carried out. Compound [ ] is a known useful insecticide. Next, the present invention will be explained with reference to Examples, where parts are by weight. Example 1 Cis-0-(1-carboisopropoxy-1-
Production of propen-2-yl)-thionophosphoric acid dichloride: 144.2 g (1 mol) of acetoacetic acid isopropyl ester was mixed with 169.4 g of thiophosphoryl chloride at 0°C.
in chloroform, followed by 22.8 g (0.1 mol) of benzyltriethylammonium chloride. A 0.2 aqueous solution of 40 g of sodium hydroxide is added to the octopus mixture kept at 0°C with vigorous stirring and stirring is continued at 0°C for 15 minutes. The chloroform layer is allowed to settle and then separated in a separatory funnel, washed with 0.2 liters of ice-cold water and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure on a rotary evaporator, the residue is subjected to high vacuum distillation at 10 ⁻⁴ mmHg (bath temperature 50° C.) to obtain 227 g (corresponding to a yield of 82%) of the title compound. No trans isomer was found in the residue.
Purity is tested by thin layer chromatography on a silica gel plate using n-hexane/acetone (4:1) as eluent and visualization by spraying the sample with an alkaline permanganate solution. The Rf values of the title compound and starting materials are as follows. cis-0-(1-carboisopropoxy-1-
propen-2-yl)-thionophosphoric acid dichloride,
Rf=0.66. 0,0-bis-(1-carboisopropoxy-
1-propen-2-yl)-thionophosphoric acid chloride, Rf=0.52. Acetoacetic acid isopropyl ester, Rf = 0.32. If an oily residue is obtained after evaporation of the solvent, it is filtered through a filtering agent such as Hyflo. The title compound adhering to Hyflo is washed out by treatment with petroleum ether in which it is dissolved. Example 2 Cis-0-(1-carboisopropoxy-1-
Preparation of propen-2-yl)-thionophosphate dichloride: 195 g (1.15 mol) of thionophosphoryl chloride are dissolved in 1.2 ml of chloroform. 22.8 g of benzyltriethylammonium chloride is added to the octopus solution kept constant at -5 DEG C. with good stirring, and 240 ml (0.1 mol) of a 20% aqueous sodium hydroxide solution is added in a slightly exothermic reaction over 10 minutes. Immediately thereafter, 144.17g of acetoacetic acid isopropyl ester
(1 mol) is added dropwise over 30 minutes at -5°C. Stirring was continued for an additional 1/4 hour at 0° C. and the process was completed as described in Example 1 to yield 218 g of the title compound (yield 78.5
%). No trans compounds were found. Cis-0-(1-
Carboisopropoxy-1-propen-2-yl)-thionophosphoric acid dichloride at 43℃/
Distill at a high vacuum of 5×10 ^-5 mmHg. n ²⁰ _D =
1.5078. The cis and trans title compounds are distinguished from the substituents of the predominantly vinyl double bond compound by their NMR signals. NMR (δ, ppm in CDCl ₃ ) Cis-0-(1-carboisopropoxy-1-
propen-2-yl)-thionophosphoric acid dichloride,
= CH5.9 multiplet; CH ₃ C = 2.52 ppm. trans-0-(1-carboisopropoxy-
1-propen-2-yl)-thionophosphoric acid dichloride, = CH5.62 multiplet; CH ₃ C = 2.20 ppm. Example 3 Cis-0-(1-carboisopropoxy-1-
Production of propen-2-yl)-0-methyl-thionophosphoric acid chloride: 165 g (1
mol) in 500 ml of chloroform. 57 g (0.25 mol) of benzyltriethylammonium chloride was added with stirring at 0°C, followed by 144 g (1 mol) of isopropyl acetoacetate at 0°C.
Add while stirring vigorously. 1 mol of 20% aqueous sodium hydroxide solution is subsequently added dropwise over 1/2 hour at the same temperature and the mixture is stirred for a further 1/4 hour at 0.degree.
Separate the chloroform layer with 0.2 ml of ice-cold water in a separatory funnel.
Wash it for a while. After drying over sodium sulphate and evaporating the solvent under reduced pressure on a rotary evaporator, 205 g (corresponding to a yield of 75%) of the title compound are obtained. The purity of the product is tested by gas chromatography. Gas chromatography testing showed virtually pure cis-0-(1-carboisopropoxy-1-propen-2-yl)-0-methyl-thionophosphoric acid chloride. Purity tests are also carried out by thin layer chromatography on silica gel plates using n-hexane/acetone (4:1) as eluent and visualization by spraying the sample with alkaline permanganate solution. The title compound is distilled at high vacuum. Boiling point 67°C/0.05mmHg, ^n20D = _1.4926 . Example 4 Cis-0-(1-carboisopropoxy-1-
Preparation of propen-2-yl)-0-methyl-N-ethyl-thionophosphate ester amide: 405 ml (10 mol) of anhydrous methanol are cooled to about -5°C. 194.8 g (1.15 mol) of thionophosphoric chloride are then added and the mixture is stirred at 10° C. for about 10 minutes. Add 1.2 liters of ice-cold water and decant the mixture from the 0-methyl-thionophosphoric chloride that settles to the bottom.
Wash twice with 120 ml of ice-cold water each time. Thus obtained 0-methyl-thionophosphoric acid dichloride [165g
(1 mol)] in 500 ml of chloroform. Then benzyltriethylammonium chloride
57 g (0.25 mol) were added with stirring at 0°C, followed by 144 g (1
mol) at 0° C. with vigorous stirring. 20%
1/2 of 1 mole of sodium hydroxide aqueous solution at the same temperature
Add dropwise for an hour and stir for a further 1/4 hour at 0°C. Immediately thereafter, 129 g (2 mol) of ethylamine are added in the form of a 70% aqueous solution at -5 DEG C. over the course of 1/4 hour. The mixture is stirred for an additional 1/2 hour at 0° C., then the chloroform layer is separated in a separatory funnel and washed once with 0.2 portions of water. After drying over sodium sulfate, the solvent is evaporated off on a rotary evaporator under water jet vacuum. Place the residue under high vacuum (10 ^-4 mmHg) for 1/2 hour 70
Subject to temperature of °C. Then petroleum ether (boiling range
100-125℃). The ether layer containing the title compound was evaporated on a rotary evaporator under water jet vacuum followed by high vacuum distillation for 1/2 hour to give 199 g (corresponding to a yield of 69%) of the title compound with a purity of at least 90%. can get. 87～89
It can be distilled at ℃/5×10 ^-3 mmHg. ^n20D ₌ 1.495. Example 5 Cis-0-(1-carboisopropoxy-1-
Preparation of propen-2-yl)-thionophosphate dichloride: 97.5 g (0.57 mol) of thiophosphoryl chloride are dissolved in 0.6 chloroform. 17.8 g (0.05 mol) of benzyltributylammonium chloride was added with stirring while the solution was cooled and maintained at -5°C, then 120 ml of 20% aqueous sodium hydroxide (0.6 mol) was added with a slightly exothermic reaction. Add over 10 minutes. Immediately thereafter, 72.1 g (0.5 mol) of isopropyl acetoacetate are added dropwise and stirred for 15 minutes at 0° C. to complete the isolation according to the procedure described in Example 1. 121.8 g of the same product obtained in Example 2
(corresponding to a yield of 87.7%) was obtained, and no detectable amount of trans isomer was contained. Example 6 Cis-0-(1-carboisopropoxy-1-
Preparation of (propen-2-yl)-O-methyl-N-ethyl-thionophosphate ester amide: O-methyl-thionophosphate chloride (165 g, 1 mol) obtained as described in Example 4 was dissolved in 500 ml of chloroform. dissolve. The solution was cooled to 0°C, 144 g (1 mol) of acetoacetic acid isopropyl ester,
Next, 85g of tetrabutylammonium hydrogen sulfate.
(0.25 mol), is added with stirring. Finally, 0
1.5 mol of 20% aqueous sodium hydroxide solution is added over 1/2 hour with vigorous stirring at °C. Stir for an additional 1/4 hour at 0°C, then rapidly cool to -5°C, then immediately while maintaining the temperature at -5°C.
129 g (2 moles) of ethylamine as a 70% aqueous solution
Add. It is then stirred for an additional 1/2 hour at 0° C. and isolated as described in Example 4. Example 4
209 g of a product (corresponding to a yield of 72.5%) is obtained which is identical to that of . Example 7 Preparation of cis-0-(1-chloro-1-carboisopropoxy-1-propen-2-yl)-thionophosphoric acid dichloride: 56 g (0.33 mol) of thionophosphoryl chloride and α in 0.6 chloroform -To a solution containing 53.6 g (0.3 mol) of chloroacetoacetic acid isopropyl ester, benzyltriethylammonium chloride is added at 0°C and then over 10 minutes, with vigorous stirring (slightly exothermic reaction), 20%
Add 72 ml of aqueous sodium hydroxide solution (0.36 mol). Continue stirring at 0°C for an additional 15 minutes. Then separate the chloroform phase and add 0.2 mL of ice-cold water using a separatory funnel.
and dry with anhydrous sodium sulfate. After the solvent was evaporated under reduced pressure using a rotary evaporator, the residue was evaporated again under reduced pressure (10 ^-4 mmHg) at 50
Dry at °C. 77.6 g of the title compound (corresponding to a yield of 83%) without contaminating the trans isomer is 10 ^-3 mmHg, 52
It can be distilled at °C (n ²⁰ _D =1482). This cis compound is identified by the NMR signal, particularly by the presence of a CH ₃ C= doublet at 2.65 ppm (1=6 cps). This doublet for trans compounds is at 2.4 ppm. Example 8 Cis-0-(1-carboisopropoxy-1-
Preparation of propen-2-yl)-thionophosphate chloride: To a solution of 33.9 g (0.2 mol) of thionophosphoryl chloride in 0.25 chloroform is added 2.8 g (0.2 mol) of isopropyl acetoacetate at 0°C. Add 8.4 g of tetraphenylphosphonium bromide [(C ₆ H ₅ ) ₄ P ⁺ Br ^- ]. Next, while stirring vigorously and keeping the temperature at 0°C, a solution containing 8.0 g of sodium hydroxide in 40 ml of water is added. Continue stirring for 15 minutes (at 0°C). The chloroform layer is separated, washed with 40 ml of water, dried over anhydrous sodium sulfate, distilled and the semi-solid residue is extracted with ether. 50g of the title compound (yield
90.2%) is obtained in almost pure form.
This compound shows the same properties as the product of Example 2. Example 9 Cis-0-(1-carboisopropoxy-1-
Preparation of propen-2-yl)-thionophosphate dichloride: 1.44 g (0.01 mol) of isopropyl acetoacetate is added to a solution of 1.69 g (0.01 mol) of thionophosphoryl chloride in 25 ml of chloroform at 0°C.
and the formula:

5.3g of crown ether which is 18-crown-6 of [Formula]
Add. A solution containing potassium hydroxide in 2 ml of water is then added over a period of 15 minutes at 0°C. After stirring for a further 15 minutes, the phases are separated and the organic phase is washed with water, dried over sodium sulfate and distilled. The residue is separated from the catalyst by extraction with ether. residue obtained from ether
Thin layer chromatography of 2.4 g (corresponding to a yield of 86.6%) yields a single spot of the title product adjacent to a spot showing traces of unreacted acetate. Example 10 Repeat the steps of Example 9. However, instead of the crown ether of 18-crown-6, the formula: Use 7.2 g of dibenzo-18-crown-6 crown ether. 2.3 g (corresponding to a yield of 83%) of the product was obtained and subjected to thin layer chromatography, and the trans isomer (less than 5% of the product) was found near the spot showing traces of unreacted acetate. Rf＝
Major spots of the title product of Example 9 were obtained with only a few spots of 0.48). As mentioned above, in the method of the present invention, compound [] is reacted with compound [] in a water-organic two-phase system in the presence of an alkali and a phase transfer catalyst, thereby producing compound [] in high yield and purity. It is characterized by being produced stereospecifically. For example, according to the method of the invention acetoacetic acid isopropyl ester [:
When R ₁ = CH ( _{CH 3 ) 2 ;} O
-(1-carboisopropoxy-1-propene-
2-yl)thionophosphoric acid dichloride [:R ₁ =CH
(CH ₃ ) ₂ ; X=H; Y ₁ = Y ₂ = Cl] is the apparent yield of approx.
It can be obtained with a purity of about 94-97% and a purity of about 90-92% (therefore, the yield of pure product is about 85-89%). Since the target compound [ ] is obtained in high purity in this way, it can be reacted with methanol and then ethylamine in the same reactor without further purification, making it itself useful as an insecticide, acaricide, and nematocide. Propetamphos can be produced. Furthermore, the purity of the final product propetamphos is approximately 90%, and the total yield from acetoacetic acid isopropyl ester can reach approximately 85%. If it has such high purity, it can be used as it is as a final product, which has the advantage of not requiring any special purification process. of the target substance [] when the same starting materials [] and [] as above are used and they are reacted on an industrial scale in the presence of a base according to the conventional method (i.e. without the use of a phase transfer catalyst). The apparent yield is around 80% at most, and the purity is also 80%.
(therefore the yield of pure product is approximately 65%)
below). And, as above, this compound []
When used as is and reacted with methanol and then ethylamine, the maximum purity of propetamphos obtained is less than 80%. With such purity, it cannot be used as a final product, and a purification process is required. It is clear that purification at the propetamphos stage is disadvantageous, and purification must be performed at the target substance stage to increase its purity. In any case, the necessity of such a purification step is not desirable as an industrial production method.

Claims (1)

[Claims] 1 Formula: [In the formula, R ₁ is C ₁ to C ₅ alkyl, X is hydrogen,
Represents chlorine or bromine. ] A compound represented by the formula: [In the formula, Y ₁ represents C ₁ to C ₅ alkoxy, chlorine or bromine, Y ₂ represents chlorine or bromine, and Y ₃ represents chlorine or bromine. ] It is characterized by condensing the compound represented by the following in an aqueous-organic two-phase system in the presence of an alkali and a catalytic amount of a phase transfer catalyst. formula: [In the formula, R ₁ , X, Y ₁ and Y ₂ have the same meanings as above, and -CH ₃ and -COOR ₁ groups are crotonic acid moieties, and one is in the cis position with respect to the other. ] A method for producing the compound shown in 2. The method according to item 1 above, wherein the phase transfer catalyst is a quaternary ammonium or quaternary phosphonium catalyst. 3. The method according to item 2 above, wherein the phase transfer catalyst is a tetra( _C1 - _C20 )alkyl or benzyltri( _C1 - _C20 )alkyl quaternary ammonium salt. 4. The above-mentioned items 1 to 3 in which the reaction is carried out at -10 to +25°C
The method described in any of the paragraphs.