KR800001183B1 - Process for 1,2,4-triazole phosphoric esters - Google Patents

Abstract

Title compds. (I; R1 = C1-5 alkyl; R2 = OR1, R1, C6H3, NHR1, N(R1)2; X = O, S; R3 = phenyl; R4 = vinyl, halovinyl, polyhalovinyl, C1-4 alkyl, C1-4 O-alkyl, C1-4 S-alkyl, acetyl, cyclohexenyl, benzoyl), useful as insecticide, were prepd. by treating 1-phenyl-3-R4-1, 2, 4-triazole-5-on(or thion)(II) with alkali followed by reacting O,O-dialkyl-(thio)-phosphoryl - chloride. Compd.(II) was prepd. by cyclizing α-amino-α-R4-formylidene-phenylydrazine, obtained by treating α-chloro-α-R4-formylidene phenyl hydrazine with ammonia, with phosgene or thiophosgene.

Description

Preparation of 1,2,4-triazole phosphate ester

The present invention relates to a novel process for producing 5-hydroxy (or mercapto-)-1,2,4-triazoles containing phosphorus in its acid moiety. More specifically, the present invention is useful for eradication of orthoptera, aphids, diptera, coleoptera, lepidoptera, triumphalus and worms, 1, The present invention relates to a process for preparing phosphorus esters of oga derived from novel 5-hydroxy (or mercapto) -1,2,4-triazoles substituted at the 3-nuclear position.

Among thiophosphates derived from variously substituted 3-hydroxy-1,2,4-triazoles at the 1 and 5 positions of the ring, various compounds have been shown to exhibit pesticidal effects.

Among them, the following two compounds are commercially available to exterminate pests, namely, they exhibit pesticidal action by contact and feeding and are sold by the German company Chast, and have the following structural formula as described in South African Patent No. 6,803,471. Insecticide Triagophos

Diethyl- (isopropyl-5-chloro-1,2,4-triazole, manufactured by Wabargai Company and described in German Patent No. 2,262,015 and represented by the following structural formula valid for the pest structure in soil: 3-yl) -phospho-thionate (Miral, trade name).

Structural formula as described in US Pat. No. 3,689,500

Derivatives of 5-hydroxy-1,2,4-triazole, such as diethoxy-phosphoro-thioate of 1-methyl-3-phenyl-5-hydroxy-1,2,4-triazole represented by Is less interested.

The inventors and the like have the following general formula (I)

(여기에서 R⁵는 OH,

Cl, S-R¹, N(R¹)₂NHR¹이다.)(Wherein R ¹ is an alkyl group having 1-5 carbon atoms, R ² is OR ¹ , R ¹ , C ₆ H ₅ , NHR ¹ , N (R ¹ ) ₂ X is O, S, and R ³ is H, alkyl having 1-5 carbon atoms, C ₆ H ₅ benzyl, alkenyl having 2-6 carbon atoms, alkynyl having 2-6 carbon atoms, R ⁴ is halovinyl, polyhalovinyl, vinyl, an alkyl group having a vinyl, C ₁ _C ₄ substituted aryl, O-alkyl group having a C ₁ _C _4, 6- alkyl groups having a C ₁ _C _4: haloalkyl, acetyl, cyclohexenyl, benzoyl,

Where R ⁵ is OH,

Cl, SR ¹ , N (R ¹ ) ₂ NHR ¹ ).

으로 표시되는 오가의 인에스테르가 광위의 작용스펙트럼을 통해 살충작용을 갖는 것을 발견하였는데, 그 이유는 이들 화합물들이 오로톱테라, 진디, 쌍시류, 클레오프테라, 레피돕테라에 대해 매우 활성이 좋으며 살개선충제 및 살사충제로서 유용하며, 이와 동시에 온혈동물에 대해 저독성을 나타냄을 발견했다. 가장 활성인 몇몇 화합물에서, 이 독성은 트리아조포스 또는 시판되는 유사화합물 보다 훨씬 낮았다.

It was found that the phosphate esters of Oga represented by the insecticide have a pesticidal effect through the working spectrum of the light beam, because these compounds are very active against ortoptopera, aphids, twins, cleopterra, and repidodotera. It has been found to be useful as an insecticide and insecticide, and at the same time exhibits low toxicity to warm blooded animals. In some of the most active compounds, this toxicity was much lower than triazophos or commercially available analogs.

Derivatives of 5-hydroxy (or 5-mercapto) -1,2,4-triazole wherein R ³ represents a phenyl group are the αchloro α-substituted formyls described in Italian Patent No. 998,314, patented in the name of the applicant. Starting from denphenylhydrazine and treated with ammonia as shown in the following scheme, the amino-derivatives produced by phosgene or thiophosgen are concentrated to give the desired triazole compounds, which are prepared by conversion to salts in alkaline media.

If R ⁴ contains a functional group, various reactions known in the organic chemical system can be used to introduce another reactor (see Example 6) into the triazol-yl (or thion) itself side chain, and so Using a typical imagination of an acetyl group from 1-phenyl-3-acetyl-1,2,4-triazol-5-one, it is reduced to a CO group to produce the corresponding alcohol, which is treated with thionyl chloride, The compounds described in were prepared.

Triazoles, wherein R ³ is an alkyl group, are concentrated by aldehyde R ₄ -CHO to 2-alkyl- (thio) -semicarbazide, followed by treatment with (thio) -semicarazone, and cancellation in glacial acetic acid according to the following scheme. And prepared in an alkaline medium as described above.

The reaction vessel assumed in the above reaction scheme is described in Tetrarahedron Letters 28 (1971), page 2669, where R ⁴ is an aryl group and X is zero.

The inventors have found that, in contrast to the former, when R ⁴ is a vinyl group, the latter compound can be attacked by cancellation, which is replaced by a series of addition and removal reactions. More specifically, if the starting material aldehydes contain cancellation and other halogen atoms at the β-position, they may be substituted by the cancellation atoms during the cyclization reaction through a series of possible reaction steps described below for illustrative purposes only.

Depending on the temperature conditions, the reaction is a reaction which forms predominantly only a single cyclic compound containing the same (halo) vinyl group of the starting material aldehyde or a cancel atom at the vinyl position of the triazole compound derived as evident in Examples 8 and 9. It can be performed to form a product containing or a mixture of these products.

The vinyl group at the 3-position of the 1-phenyl-1,2,4-triazole (5) -one (or thion) compound, as described in the first reaction formula (page 5, compound 6) on an acetyl group, It may also be prepared starting from 1-phenyl-3-acetyl-1,2,4-triazol-5-one (or thion).

In addition, the inventors of the general formula

(여기에서, R⁵는 OH,

Cl, S-알킬, O-알킬, NH-알킬, N(알킬)2를 나타냄) ;

알킬이고 ; X는 O, S임)으로 표시되는 세미카아바존의 환형화를 다음과 같은 반응식에 의하여Wherein R ³ is H, alkyl having 1-5 carbon atoms, C ₆ H ₅ , benzyl, alkenyl and alkynyl, R ⁴ is halovinyl, polyhalovinyl, vinyl; aryl, alkyl, 0- Vinyl groups substituted with alkyl, S-alkyl, haloalkyl, cyclohexenyl, acetyl, and benzoyl groups;

Wherein R ⁵ is OH,

Cl, S-alkyl, O-alkyl, NH-alkyl, N (alkyl) 2);

Alkyl; X is O, S) to the cyclization of semi-carbazone represented by the following reaction scheme

It has been found that it can be done in the presence of ferric chloride.

As described above, even when the R ⁴ group contains an olefinic double bond capable of being attacked by a canceling atom, triazolone (or thion) can be obtained directly in a state of high purity. It proved superior to other methods.

This reaction is carried out in a polar solvent, preferably in acetic acid at boiling point.

The properties of 1,2,4-triazol-5-one produced by one of the methods described above are shown in Table 1 below.

TABLE 1

1,2,4-triazol-5-one produced by the method of the present invention has the following general formula;

※ The melting point is not accurate.

1,2,4-triazole- (5) -one (or thione) in the presence of a base can be converted to their alkaline salts and reacted with a suitable (thio) -phosphoryl chloride to yield the following general formula (I) The triazolyl- (thio) -phosphate represented by can be manufactured.

By this method, 0,0-dialkyl-0- (1-R ³ -3-R ⁴ -1,2,4-triazol-5-yl) -thiophosphate shown in Table 2 described below is obtained. Was prepared.

The target compounds of the present invention have a broad spectrum of action for a number of parasitic arthropods as is apparent in Table 5. Because of their nature, they have practical advantages over most known pesticides. In addition, these compounds are toxic to warm-blooded animals despite their activity on arthropods.

Oral dosing for albino rats has been shown to be greater than 1200 mg / kg for compound M8174.

As an example, the absolute harmlessness identified in rats with the representative compound M7852 at a dose of 800 mg / kg was compared with the characteristic value LD ₅ for two commercial triazolyl-phosphate insecticides. In order to further compare the pesticidal effects of the novel compounds, the present inventors have formed the compounds listed in US Pat. No. 3,689,500 and found that they exhibit low toxicity to mammals.

In this compound (M8172), the present inventors evaluated the effect on various poisonous animals, and the effect of the compound (M8174) cited by the present inventors among the compounds described in the foregoing patents while reducing the dose.

The results listed in Table 4 show a better effect of compound M8174 on ortopera, lepitopera, colooptera, twins and worms, triumphal larvae.

From the results shown in Tables 4 and 5, it was found that the target compounds according to the present invention are very effective as insecticides and nematode insecticides and insecticides against ortopera, aphids, twins, choloptera and lepidodotera. These compounds were also found to be much less toxic to warm-blooded animals than Triajo phos and Miral (see Table 3).

TABLE 3

TABLE 4

TABLE 5

The following examples are described to specifically illustrate the present invention.

Example 1

Preparation of 1-phenyl-3-acetyl-1,2,4-triazol-5-one;

80 ml of an aqueous solution of NH ₃ (32% bw) (1.32 mol) was mixed with 500 ml of ethanol, and 60 g (0.305 mol) of a solution of α-chloro-α-acetyl-formylidene-phenylhydrazine (1) was added little to this solution. Added. After the addition was complete, the mixture was stirred for 2 hours at room temperature. Insoluble α-amino-α-acetyl-formylidene-phenylhydrazine (2) (48 g) was filtered and washed with 200 ml of water. (Yellow solid, melting point 182-184 ℃)

42.5 g (0.24 mol) of α-amino-α-acetyl-formylidene-phenylhydrazine was dissolved in 300 ml of benzene, and 57 ml (0.72 mol) of pyridine was added to the suspension, followed by 10% concentration (% b.vol. 40 ml of 0.36 mol of benzene solution was added dropwise and maintained at a temperature of 15-20 占 폚.

After the addition was complete, the mixture was stirred at room temperature for 30 minutes, and then 100 ml of H ₂ O and 10 ml of concentrated hydrochloric acid were added to the filter. The whole mixture was stirred at room temperature for 2 hours. The insoluble material was filtered only with a porous grid and washed with H ₂ O to give 0.25 g of 1-phenyl-3-acetyl-1,2,4-triazole (3). (Melting point, 174-176 ° C))

Example 2-4: The reaction was carried out as described in Example 1: 1-phenyl-3-benzoyl-1,2,4- starting from -α-chloro-α-benzoyl-formylidene-phenylhydrazine Triazole (5) -one is prepared,

1-phenyl-3- (methylthio-acetyl-1,2,4-triazol (5) -one is prepared starting from -α-chloro-α-methylthio-acetyl-formylidene-phenylhydrazine ,

1-phenyl-3- (carboethoxy) -1,2,4-triazol (5) one was prepared starting from -α-chloro-α-carboethoxy-formylidene-phenylhydrazine. .

Example 5

reaction

2,3 g of 1-phenyl-3-methylthioacetyl-1,2,4-triazole (5) one suspended in 40 ml of methanol was treated dropwise with a solution of 0.3 g of NaBH ₄ dissolved in 5 mg of water. The reaction mixture was stirred for 1 hour, then 0.5 ml of concentrated hydrochloric acid was added, and the solvent was removed.

The residue was taken up in 20 ml of water and 0.5 ml of concentrated hydrochloric acid, the aqueous solution was extracted with ethyl acetate (3 x 30 ml), and the organic phase was anhydrous treated with anhydrous Na ₂ SO ₄ .

The solvent was removed under reduced pressure and the solid residue was crystallized from benzene (10 ml) to give 1-phenyl-3- (1-hydroxy-2-methyl-mercapto) -ethyl-1,2,4-triazole (5 1 g of) -one (ivory solid, melting point, 102 ° -104 ° C.) (M8173) was prepared.

Example 6

The reaction was carried out in the same manner as described in Example 5, starting with 70 g of 1-phenyl-3-acetyl-1,2,4-triazole (5) -one, followed by 1-phenyl-3 (1-hydroxy). Ethyl) 1,2,4-triazole (5) -one 56 g was obtained (melting point, 149 ° -150 ° C.) (M8262).

Example 7

16 g of the product obtained in the same manner as described in Example 6 above was added dropwise while stirring 7.6 ml of SOCl ₂ to a solution of 350 ml of chloroform (CH Cl ₃ ). This solution was stirred at room temperature for 2 hours and then decanted in 150 ml of water. Separated on chloroform and acidified. After the solvent was removed, 1-phenyl-3 (1-chloroethyl) -1,2,4-triazol (5) -one was obtained (melting point, 159-160 ° C.) (M8085).

5.5 g of the product thus prepared was dissolved in 150 ml of benzene, gently warmed in the presence of 7.5 g of triethylamine, and dehydrogenated. After the completion of the reaction, 40 ml of water and 10 ml of concentrated hydrochloric acid were added to the reaction mixture.

The benzene layer was separated, washed with water and anhydrous treated with anhydrous Na ₂ SO ₄ . The solvent was removed in vacuo until reaching 50 ml. Slight cooling allowed to separate 1-phenyl-3-vinyl-1,2,4-triazole (5) -one 2 (melting point, 200 ° C.) (M8263)

Example 8

1-methyl-3-tribromovinyl-1,2,4-triazol (5) -one and 1-methyl-3- (α-bromoβ.β-dichlorovinyl) -1,2,4- Preparation of Triazole (5) -one.

3 g (0.0153 mol) of 1- (β.β-dichloroacylidene) -2-methyl-semicaavazide (1) was dissolved in 15 ml of glacial acetic acid, and 1.6 ml of cancellation was then slowly added to this solution. This mixture was then heated (slight reflux) for 30 minutes, then cooled and 150 ml of H20 was added. Then extracted with ethyl acetate (2 times 50 ml). This ethyl acetate solution was washed with 50 ml of H20 and a saturated solution of NaHCO ₃ (3 times with 40 ml). Then it was dried over anhydrous Na ₂ SO ₄ , filtered, and then the solvent was removed.

The residue was recovered with 50 ml of 10% NaOH aqueous solution and the entire mixture was heated to initial boiling point. This mixture was then cooled and filtered. This filtrate was made acidic with concentrated hydrochloric acid HCl. The residue was separated into a yellow solid, which was extracted with ethyl acetate (2 x 50 ml).

The organic solution was then washed with water (50 ml), anhydrous with anhydrous Na ₂ SO ₄ , and the solvent was removed. 1.9 g of a yellow solid were obtained, which was crystallized with benzene (30 ml) to yield 1 g of a nearly white crystalline solid (melting point, 161-163 ° C). This solid consists of a mixture of compounds (2) and (3), as evident in the mass spectrum, and two molecular peaks of about the same intensity in the spectrum of electricity [(2): M ⁺ = 361.7, (3 ): M ⁺ 273].

By elemental analysis data, it was calculated that this mixture consisted of 56% of (3) compound and 44% of (2) compound.

Example 9

Preparation of 1-methyl-3- (β.β-dichlorovinyl) -1,2,4-triazole- (5) -one

9.7 (0.0494 mole) of 1- (β.β-dichloroacylidene) -2-methyl-semicaavazide (1) was dissolved in 50 ml of glacial acetic acid.

This solution was gently refluxed while 2.8 ml (0.054 mol) of cancellation was added dropwise very slowly. After completion of the dropwise addition reaction, the solution was naturally cooled.

Acetic acid solution was added dropwise to a suspension of 120 g of NaHCO ₃ suspended in 300 ml of H20. After the foam subsided, 250 ml of ethyl acetate was added and the whole mixture was stirred.

The organic phase was separated, dried over anhydrous Na ₂ SO ₄ , the solvent was evaporated to reduce the volume to 40 ml, then evaporation was stopped and the solution cooled to about 0 °. The yellow precipitate was filtered through a porous septum.

2 g of 1-methyl-3 °-(β.β-dichlorovinyl) -1,2,4-triazole (5) -one (2) were obtained. (Melting point after recrystallization with ethyl acetate = 215-216 ° C)

Example 10-11

Starting from the appropriate 1- (polyhaloacylidene) -2-methylsemica abazide and following the method described in Example 9, the following 1,2,4-triazole- (5)-warms were Manufactured. :

-1-methyl-3- (β.β-dibromovinyl) -1,2,4-triazol- (5) -one

-1-methyl-3- (tribromovinyl) -1,2,4-triazol- (5) -one

Example 12

Preparation of 1-methyl-3- (β.β-dichlorovinyl) -1,2,4-triazol- (5) -one using ferric chloride

1- (β.β-dichloroacylidene) -2-methyl-semicaabage in which 49 g (0.18 mol) of a 6-fold ferric chloride (FeCl ₃ , 6H ₂ O) dissolved in 100 ml of water was dissolved in acetic acid (50 ml). To 17.5 g (0.089 mol) of a solution of de (1). The resulting solution was heated at reflux for 3 and a half hours, then it was naturally cooled and 150 ml of water was added.

This solution was then cooled at about 0 ° C. (ice water bath). 12 g of 1-methyl-3- (β.β-diclovinyl) -1,2,4-triazol-5-one (2) was precipitated. (After determining with ethyl acetate, melting point, 215-216 ° C. ).

Example 13

Preparation of 1-methyl-3- (β.β-dimethylvinyl) 1,2,4-triazol-5-one

To a solution of 10.6 g (0.119 mol) of 2-methyl-semica abazide (2) dissolved in acetic acid (100 ml) was added dropwise 10 g (0.119 mol) of β.β-dimethyl-acrolein (1). The reaction mixture was stirred at 50 ° C. for 15 minutes and then added to a solution of 64.2 g (0.237 mol) of FeCl ₃ 6H ₂ O dissolved in 60 ml of water.

The whole mixture was stirred at 75 ° C. for 3 hours, then it was decanted into water (400 ml) and extracted with ethyl acetate (2 × 150 ml). The organic phase was separated, washed with water, washed with saturated NaHCO ₃ solution and dried over anhydrous Na ₂ SO ₄ .

The solvent was removed to give 4 g of 1-methyl-3- (β.β-dimethylvinyl) -1,2,4-triazol-5-one (3). (Melting point, 144-146 ° C)

Example 14

Preparation of 1-methyl-3- (β-chloro-β-methoxyvinyl) -1,2,4-triazol-5-one

6.8 g (0.035 mol) of 1-methyl-3- (β.β-dichlorovinyl) -1,2,4-triazol-5-one (1) in a round bottom hulask equipped with a reflux condenser, 50 ml of methanol And 8 g of KOH were introduced. The reaction mixture was stirred for 5 hours at reflux temperature, and then it was decanted into water (150 ml) and concentrated hydrochloric acid (20 ml), which was extracted with ethyl acetate (3 x 100 ml). The organic phase was dried over Na ₂ SO ₄ and the solvent was removed. 3 g of 1-methyl-3- (β-chloro-β-methoxyvinyl) -1,2,4-triazol-5-one (2) was obtained. (Melting point, 198-199 ° C.)

Example 15

Preparation of 1-methyl-3- (2-chloro-1-cycloexenyl) -1,2,4-triazol-5-one

50 ml of acetic acid was added to a solution of 27 g (0.1 mol) of FeCl ₃ 6H ₂ O dissolved in 30 ml of water. The resulting solution was stirred at 100 ° C., while a solution of 10.8 g (0.05 mol) of semikabazone (1) dissolved in 50 ml of acetic acid was added dropwise within 2 hours. The heating was continued for another 1 hour, then the solution was cooled, 300 ml of water was added, and extracted with chloroform (2 x 200 ml).

The chloroform extract was separated, washed with saturated NaHCO ₃ solution and dried over anhydrous Na ₂ SO ₄ . The solvent was removed to obtain 4.5 g of an oily substance. The oil is left to solidify and the solid is washed with diethyl ether to give 1-methyl-3- (2-chloro-1-cycloexetyl) -1,2,4-triazol-5-one (3). ) (Melting point, 183-185 ° C) 4 g was obtained.

Elemental analysis: Cl, Theoretical value: 16.60%, Found: 16.76%

Example 16

Preparation of 0,0-diethyl-0- (1-methyl-3-tribromovinyl-5-triazolyl) -thiophosphate.

3.82 g (0.01 mol) of 1-methyl-3-tribromovinyl-5-hydroxy-1,2,4-triazole (1) (sodium salt) was dissolved in 100 ml of acetyl.

1.6 ml (0.01 mol) of 0,0-diethylchlorothiophosphate was added to this solution. This solution was then heated to 55 ° -60 ° C. for 2 hours. Acetone was then evaporated and the residue was dissolved in 100 ml of diethyl ether and 50 ml of H ₂ O. Stir this mixture. The organic phase was separated, dried over anhydrous Na ₂ SO ₄ and the solvent was evaporated. Thus, 4.7 g of a yellow oil was obtained, which was purified by chromatography on silica gel using benzene as a developing agent to obtain 0,0-diethyl-0- (1-methyl-3-tribromovinyl-5-triazolyl 3.5 g of) -thiophosphate (3) was produced. (White solid, melting point 45 ° -50 ° C.) Another 0,0-diethyl-0-triazolyl-thiophosphate shown in Table 2 was prepared in a similar manner.

Example 17

1-methyl-3- (β.β-dichlorovinyl) -5-hydroxy-1,2,4-triazole (sodium salt) and 0,0-dimethyl-chloro 0,0-dimethyl-thiophosphoric acid ester (M8373) of 1-methyl-3- (β, β-dichlorovinyl) -5-hydroxy-1,2,4-triazole starting from thiophosphate ( Melting point, 102 ° -103 ° C). Elemental Analysis: Cl (Theoretical Value): 22.30%; Found: 22.45%

Example 18

Biological Effect Test of Compounds According to the Present Invention:

1) Biological effects on macrophages euphorbiae (aphids):

Potted potato plants were infested with aphid females and sprayed with aqueous aqueous dispersions (see Table 5) of tested and degraded products after several days.

Deaths were assessed as percentages after 24 hours of treatment (untreated plants = 0).

2) Biological Effects on Pieris brassicae (Lapidotera): Cut cauliflower leaves were sprayed with aqueous dispersions of compounds tested and degraded (see Table 5). After drying, the leaves were infested with larvae 5 days old. The mortality of the larvae was measured 48 hours after the treatment (untreated leaves = 0).

3) Biological Effects on Leptinotasar decemlineata (Coleoptera):

Potted young potato plants were infested with larvae at 4 days of age, and then sprayed with aqueous dispersions of the tested and degraded compounds (see Tables 4 and 5). Mortality percentage (untreated young plants = 0) was measured 48 hours after treatment.

4) Biological effects on Culex pipiens (twins):

The mosquito larvae of the 3rd and 4th stages were put into the glass containing the aqueous dispersion (refer to Tables 4 and 5) of the compound tested and deteriorated. The mortality percentage of the larvae (glass with pure water = 0) was measured 24 hours after treatment.

5) Biological effects on Tetranichus urticae (nematode):

The disk of soybean leaves was infested with an insecticidal insect, and then sprayed with an aqueous dispersion of the compounds tested and degraded (see Tables 4 and 5). Mortality percentage (untreated leaf disc, mortality = 0) was measured 24 hours after treatment.

6) Biological Effects on Tetraatures Urtica

Small discs of soybean leaves were infested with ameliorated arachnids, and then sprayed with aqueous dispersions of the compounds tested and degraded (see Table 5). Mortality percentage (untreated leaf disc, mortality = 0) was measured 6 days after treatment.

7) Biological effects on Spodoptera littoralis (Lepidotera).

The cut tobacco leaves were sprayed with a water soluble spray of compounds (see Tables 4 and 5) to test and deteriorate. After drying, the leaves were infested with larvae 5 days old. The mortality percentage of larvae (untreated larvae, mortality rate = 0) was measured 48 hours after treatment.

8) Biological effects on Meloidogyne incognita (reptiles).

The soil and sand 1: 1 mixtures were infested with newly born larvae and eggs of the worms, and treated with a uniform mixture of aqueous dispersions of the compounds tested and deteriorated (see Tables 4 and 5). The soil was then placed in plastic pots, and five days later, five small tomato plants about 20 cm tall were planted in each pot.

The results were recorded 21 days after transplantation. The spread was measured by calculating the galls formed by observing the roots of the plant out of the soil. The insecticidal effect was expressed as a percent reduction (young plants transplanted in untreated soil, effect = 0).

9) Effect on Hilemyia brassicae (twins): Partial soil was tested and treated with uniform dispersion of water-soluble dispersions of compounds (see Tables 4 and 5). The soil was then divided into two pots and four small radishes implanted in each of these pots. The plant was then infested with soil with 50 bivalve eggs in the center of the pollen. Plants were extracted from the soil, the number of larvae in the roots and soil was calculated and the results recorded 10 days after treatment.

Insecticidal effect was expressed as a percentage of reduction (plants transplanted in untreated soil, effect = 0) compared to control plants.

10) Biological Effects on Blata orientalis (Or Dottara): The bottoms and walls of the glass crystals were tested and treated uniformly with acetone solution of the compound (see Tables 4 and 5). After evaporating the solvent, each glass crystal was placed with 10 nanides, which are 80-100 days old. Then, the crystals were closed with a metal net stopper. After 24 hours of treatment, the pests were transferred to similarly shaped untreated crystals and fully nourished. Mortality percentage (untreated pest = 0) was measured 48 hours after treatment.

Claims (1)

α-chloro-α-R ⁴ -formylidene-phenylhydrazine was treated with ammonia to prepare α-amino-α-R ⁴ -formylidene-phenylhydrazine and the compound was cyclized to phosgene or thiophosgen 1 -Phenyl-3-R ⁴ -1,2,4-triazol-5-one (or thion) is prepared, treated with alkali and the appropriate 0,0-dialkyl- (thio) -phosphoryl-chloride Method for producing 1,2,4-triazole phosphate ester represented by the following general formula characterized in that the reaction with.

Wherein R ¹ is an alkyl group having 1-5 carbon atoms, R ² is OR ¹ , R ¹ , C ₆ H ₃ , NHR ¹ , N (R ¹ ) ₂ , X is O, S, and R ³ Is a phenyl group and R ⁴ is vinyl, halovinyl, polyhalovinyl, a vinyl group substituted with an aryl group, an alkyl group having 1-4 carbon atoms, a 0-alkyl group having 1-4 carbon atoms, and having 1-4 carbon atoms S-alkyl group, haloalkyl, acetyl, cyclohexenyl, benzoyl,

Wherein R ⁵ is OH,

Cl, SR ¹ , OR ¹ , N (R ¹ ) ₂ , NHR ¹ ) —CO—CH ₂ —SR ¹ —C (R ⁵ ) = CH—CH ₂ —SR ¹ ).