UA13563U - A method for the utilization of hydrazine-containing liquid rocket fuels - Google Patents

Abstract

A method for the utilization of hydrazine-containing liquid rocket fuels involves chemical modification thereof by an interaction with chemical reagent in the medium of solvent, subsequent treatment with Pb compounds, subsequent treatment of reaction mass with hydrazine-containing rocket fuels or amines or ammonia. The obtained intermediate is cyclized by carboxylic acids with formation of some salts of derivatives of 1,2,4-triazol. The latter interact with aqueous, aqueous-organic or organic medium with appropriate salts of alkaline, alkaline-earth and transition metals with formation of end power-consuming salts of derivatives of 1,2,4-triazol.

Description

Description of the invention

The useful model refers to the field of chemical technologies and is a method of processing liquid rocket propellants 2 (LPP) based on hydrazine and its M-alkyl and M,M-dialkyl derivatives to obtain energy-intensive salts of some 1,2,4-triazole derivatives. A useful model can be used for the neutralization and disposal of highly toxic substances using the resulting products as components of mixed explosives (MEDs) and polymolecular solid and unitary rocket propellants (MPPs).

The method of utilization of asymmetric dimethyl hydrazine (NDMH) by treating a 20-2595 solution of NDMH with oxalic acid in the medium of isopropyl or ethyl alcohol at a molar ratio of acid to NDMH from 1.00 to 1.05 (prototype) |Patent of Ukraine Mo18128А MKVU СО1821/16 Method of disposal of NDMH. / L.M. Kapkan,

Chervinskyi O.Yu., Vdovichenko O.M., Savossii M.V., etc.; Mo. 95041594, application no. 10.04.95, publ. 01.07.97. Bul.

Mo5 dated 31.10.97).

However, this method does not provide for the combined disposal of RRP components and their oxidizers. In addition, the disadvantages of the method are that due to the weak acid properties of oxalic acid (H»С»О), the formed salt can decompose with the release of NDMH into the environment, in addition, the authors limited the choice of solvents and also obtain diluted solutions of (CHNas)2MMN »o"NhSh»O, which requires their additional processing.

The task of a useful model is to dispose of highly toxic hydrazine-containing components of RRP in such a way as to obtain energy-intensive, less toxic salts of 1,2,4-triazole derivatives with a minimum amount of harmful waste by carrying out certain chemical transformations.

The task is solved by the fact that in the known method of disposal of highly toxic RRP - asymmetric dimethylhydrazine, which includes its chemical interaction with a reagent (oxalic acid) in a solvent medium (lower aliphatic alcohol), according to the invention, it differs in that chemical 29 modification is carried out in three stages; also utilize hydrazine, monoalkylhydrazine, M,M-dialkylhydrazines and She Aerozin-50 (a mixture of equal mass parts of NDMH and MeoNai); at the first stage, an intermediate is obtained - compounds A of the general formula

VMS(MeMeV. 2"(NH)a or БЕ2-MS(MEMEV "HMeM-SNAGI(NH) a, so z de v, B'-H, SN", SoNv; B2-H, AIK, MVV"; AIk - alkyl C.-C;; НХ-Нна), 1/2Н5804, NOZOZAIK, NOZVO»AG; a-0, 1, 2; c

Dr (Kz k- NN, SNO, gONU.OM, Nai, No; that) co

Kk h- at the second stage, the obtained intermediate is cyclized to obtain compounds B of the general formula

It's to blame

Shi 1 "Inshu va "INAU, I tn I Balko is INllh, " h-h - s pon a. cont sa i vd "Innu, yai she de Ap'-SI, Vg, I, 1/7250,4, NBZO,, NoRO,; 6-0, 1, 2.

At the third stage, the final salts of 1,2,4-triazole derivatives are obtained by the interaction of compounds B with salts of MAp 7 - the general formula с (VAZEZ) (Nap o

Ap'-MOz7, SiO/7, C(MO»)37, C(SM)57, Sh(MO2)57, Ma", (MO2)CH", in 1/21C(MO dia, (02M)oCH- S (MO), b 50 m, ch cha, shn vod sn, in ? o,n Sh a: di is o,ny: kn o, ny: I nik i g . Kzh "M au yno s mn n-m be, all of it, O Lessnnog, in О2ММНСНоСНоМ МО», О2ММНСНоМ МО», 1/2СНо(М'МО2)», В'М'МО»; c-1,2; a-1,2 where M"-ii , Ma, K, МН,, 1/2Са, 1/2Ва, 1/2Ма, 1/2Р5, 1/2На, Ad;

Moreover, at the first stage, the utilized hydrazine-containing PRPs are sequentially treated with RH reagents, then, if necessary, RBO or Pb(OH)", then, if necessary, AgSONO and, finally, AIKXX with subsequent treatment with hydrazine-containing PRPs or amine AIKMN" or MHz with isolation of the intermediate And by known methods, and 65 reagent RG belongs to the following series: С5 », СС», AIKMS5, NoMOSM, KNMSM, KoMSM, NoMS (MNIMNeM,

Naism, NZSM or M'ZSM, (НМ)бС-МН; Na!-сSI, Vg, I; M'-Ma, Gi, K, 1/2Sa, 1/2Ba, 1/2Ma.

In the second stage, intermediate A is cyclized by sequential treatment with carboxylic acid of the general formula В'СООН at a temperature of 50-1302C for 0.3-20.0 hours. and treatment with NAp solution in an aqueous, water-alcohol environment at a temperature of 80-1202C for 0.3-6.0 hours. with separation of by-products by known methods and obtaining salts in the form of solutions and/or solid state after evaporation of excess solvent.

At the third stage, the interaction of compounds B with salts of MAp 1 or with acids NAp!' is carried out in an aqueous, aqueous-organic or organic solvent at a temperature of -10-5092 for 0.1-2.0 hours, and the final salts of 1,2,4-triazole derivatives are obtained in the form of concentrated solutions and/or in a solid state after evaporation of 70 solvents , and alcohol AIKON, diethyl ether, dimethylformamide, dimethylsulfoxide, acetonitrile and/or their mixtures are used as an organic solvent.

Water and/or organic solvents, which are distilled off during the concentration of solutions of substances A, B and final salts of 1,2,4-triazole derivatives, are used at the next stage of salt synthesis.

Gases that are formed during the preparation of substances A and/or B are washed with solutions of acids НО, where М is МО».

SiO,, С(MO»)z3, ORK, M(MO)» by obtaining the corresponding salts.

It is also possible to obtain a mixture of salts of 1,2,4-triazole derivatives.

A significant difference of the declared useful model in comparison with the prototype is: - The possibility of recycling, in addition to NDMH, also monomethylhydrazine (MMH), monoethylhydrazine,

M,M-diethylhydrazine and aerosin -50; - the possibility of obtaining stable, less volatile and toxic salts of 1,2,4-triazole derivatives, which are energy-intensive substances, on the basis of usable hydrazine-containing RRP; - expanding the capabilities of the method due to: a) the use of various energy-intensive acids and oxidizing acids; b) obtaining salts by carrying out an ion exchange reaction; c) increasing the list of solvents for the salt formation reaction; d) obtaining more concentrated solutions of salts. 29 We give examples of a specific implementation of a useful model. shsh

Example 1

Utilization of "zerosin-50" and NDMH to obtain (4-dimethylamino-1,2,4-triazolyl-3)-hydrazinium dinitrate.

14g of "aerozin-50" and 5g of NDMG are to be disposed of. "Aerozin-50" is rectified by driving off NDMH, the cubic residue is 98905 hydrazine (295 - hydrazine hydrate). o 1) Preparation of 1-(2, b6-dichlorobenzylidene)-2-dimethylamino-3-amino-guanidinium chloride. (Se)

To a solution of 12.5 g of 9096 KOH in 7 Oml of 9995 methanol, add 15.5 ml of 97906 NDMH while stirring. The solution is cooled in the reactor, which is equipped with a stirrer, a drop funnel, placed in a bath, to -0-59C, and while stirring, a solution of 1 g of carbon disulfide C5 in 20 ml of methanol is added dropwise. The reaction mass "9 is stirred for another 0.5 h, kept in the cooling mixture for another 1 Ohv., add diethyl ether until the beginning of crystallization. The precipitate of potassium 2,2-dimethyldithiocarbazinate formed is filtered off, washed with cold alcohol, dried in air. Yield 29.6 g (8596).

The resulting salt is dissolved in the minimum necessary amount of water, the solution is poured into a reactor equipped with a reflux condenser, a drop funnel and a stirrer. While stirring, 20 25.00 ml of SNU is added dropwise, the reaction mass is intensively stirred at room temperature for 3-4 hours. and at 30-4020 - 1 hour, with c then cooled to 09Sb. The formed precipitate of 2,2-dimethyldithiocarbazinic acid methyl ether is filtered off, washed, and dried. Yield 19.1g (7590). The obtained compound is suspended in 50 ml of ethanol and a solution of 4.2 ml of 9895 M»N is added; in 5 Oml of ethanol.

The reaction mass is heated to 1-50-60 C and at this temperature, with intensive stirring, is kept under reflux until the formation of methylmercaptan ceases. -k The reaction mass is diluted with alcohol and heated until the 1,1-dimethylthiocarbohydrazide precipitate is completely dissolved, then 22.3 g of 2,6-dichlorobenzaldehyde is added, the volume of the solution is brought to 250 ml with hot ethanol. «sl The reaction mass is boiled under reflux for 12 hours, cooled, sediment 5r Filtered, air-dried. Output Z1.5g (8590), Tll-204-20590. b The obtained compound is added to a solution of 16.0 g of CH2 in 200 ml of absolute ethanol and boiled under reflux for 2.5 hours. The reaction mass is partially evaporated with distilled alcohol, the residue is cooled, diluted with diethyl ether until a precipitate of the product -1(2,6-dichlorobenzylidene)-5,5-dimethyl-8-methylisothiocarbohydrazide iodide is formed, which is filtered off and dried on

AIR Exit Zbg (76,590), Tll9090.

The obtained salt is dissolved in the required amount of hot water, 2.7 ml of 9895 M Na is added and heated until the release of methyl mercaptan stops. Then the reaction mass is partially evaporated under vacuum on a rotary evaporator and neutralized with 2595 ammonia water (-6-6.5 ml), cooled. The formed precipitate is filtered, washed with cold water and dissolved in 1 ml of concentrated NSI and 40 ml of water. 60 A precipitate of 1-(2,6-dichlorobenzylidene)-2-dimethylamino-3-aminoguanidinium chloride was formed, which was filtered off and dried in air. Output 16.2g (6090), Tel: 180-18296. 2) production of nitric acid salt.

The obtained salt is dissolved in 40 ml of 8595 NCOOH and refluxed for 2 hours.

The reaction mass is evaporated under vacuum with distilled HCOOH, the solid residue is dissolved in 100 ml of 5N NOSI and b5 is boiled under reflux for 1.5 hours. The reaction mass is extracted with hot benzene, the extract is separated. Then the aqueous phase is acidified with 100 ml of concentrated NH and boiled with the distillation of part of the NOSI solution for 2 hours, then cooled and extracted again with benzene. The aqueous solution is separated, if necessary, the operation with subsequent hydrolysis and extraction of free 2,6-dichlorobenzaldehyde is repeated once more. The resulting solution is partially evaporated under vacuum on a rotary evaporator, the remainder is cooled.

The resulting precipitate of 3-hydrazino-4-dimethylamino-1,2,4-triazole dihydrochloride is filtered off and dissolved in the minimum necessary amount of water. A solution of 16.4 g of RB(MO 3)2 in 7 Oml of hot water is added to this solution. The sediment of the "PHC" is filtered off, washed with ice water. The filtrate is evaporated until the volume of the residue is 25-30 ml, cooled, the remaining amount of PCI is filtered off, the filtrate is evaporated. The remainder is 15.6 bg 8590 of an aqueous solution of (4-dimethylamino-1,2,4-triazolyl-Z)hydrazinium dinitrate. 70 Example 2

Utilization of hydrazine to obtain 2,4,6-trinitroresorcinate (4-amino-1,2,4-triazolyl-3)-hydrazinium.

10.5 ml of 97905 hydrazine is subject to disposal.

10.5 ml of MoNui hydrazine 97905 is added to a solution of 9.0 g of guanidine hydrochloride in 10 ml of water. The reaction mass is heated to (-80-902C for 3.5 hours, while ammonia is intensively formed, which is absorbed by a solution of 75 2695 NMOz during external cooling, thus obtaining a solution of ammonium nitrate.

The reaction mass is cooled to Y-5-1020. The formed precipitate of triaminoguanidinium chloride is filtered off, washed with ice water, dried in air. Output 12g (9195). Tyad-237-23996,

The obtained salt is added to ZOml of 8596 NCOOH and refluxed for 2 hours.

The reaction mass is evaporated under vacuum at (-95-1009С on a rotary evaporator, driving off the excess of unreacted formic acid. The residue is dissolved in 5 Oml of 2095 NCI, refluxed for 1.5 hours. The solution is partially evaporated under vacuum on a rotary evaporator, the residue is dissolved in 50 bOml of hot ethanol, acidified with 5 ml of concentrated NH. Upon cooling, a precipitate of 3-hydrazino-4-amino-1,2,4-triazole dihydrochloride precipitates, which is filtered off, washed with cold 2-propanol, dried in air. Yield 12.8 g (80965).

The resulting salt is dissolved in 30 ml of hot water, then a sodium styphnate solution prepared from 75.4 g of Mmaon, 16.5 g of 2,4,6-trinitroresorcinol and 100000 ml of hot water is added. Upon cooling, a precipitate of 2,4,6-trinitroresorcinate (4-amino-1,2,4-triazolyl-3)-hydrazinium is formed, which is filtered off, washed with ice water, and dried. Output 22g (9196). 2,4,6-trinitrophenolate 4-amino-(1,2,4-triazolyl-3)-hydrazinium (Tdl-160-16220) and 2,4,6-trinitro-3-methylphenolate 4-amino-( ze) (1,2,4-triazolyl-3)-hydrazinium. "co

Example C

Utilization of hydrazine to obtain 5-methyl-4-amino-3-hydrazino-1,2,4-triazole dihydroperchlorate. iv)

BZml 9890 MoN is subject to disposal. so a) obtaining triaminoguanidine hydrochloride.

Into the reactor, equipped with a mechanical stirrer, a drop funnel, placed in a bath with a coolant, 3ml of 9895 MaNu is poured, then 70-8O0ml of water is added drop by drop. When cooling and stirring, add 5ml of 3495 NSI from a dropper so that the temperature does not exceed 702. Then add 42g of dicyandiamide (DCDA). The reaction mass is heated to -85-902C and kept at this temperature and stirring for 1 hour, without stirring - 1.5-2.0 hours.

The reaction mass is cooled to room temperature. The precipitate of the precipitated product is filtered off, squeezed out, washed with ice water (2 x 30 ml), dried in air. Exit bOg (8590). PTpd-237-23996,

From" b) production of chloride salt.

The obtained salt (b0 g) is dissolved in 120 ml of glacial acetic acid (NOAc) under heating and the solution is refluxed for 4 hours. The excess NOAc is distilled off on a rotary evaporator under vacuum. The viscous residue from 49 is dissolved in 200 ml of carrier medium, the reaction mass is refluxed for 1.5 hours.

Excess hydrochloric acid is distilled off under vacuum, the residue is treated with hot 2-propanol, and the salt is crystallized. Yield of 5-methyl-4-amino-3-hydrazine-1,2,4-triazole dihydrochloride 6b1g (7196). sl Trpdy-245-25126.

The obtained salt is dissolved in 15 ml of hot water, a solution of 139 g is added to the resulting solution

Me, RB(SiO,), ЗН2О in 200 ml of water with stirring. The precipitate of PCSI" is filtered, washed with ice water, the combined filtrates are evaporated under vacuum, 106 g of a solid substance containing 695 H"O is obtained, the rest is 5-methyl-4-amino-3-hydrazino-1,2 dihydroperchlorate, 4-triazole.

Example 4

Utilization of hydrazine to obtain 5-methyl-4-amino-3-hydrazino-1,2,4-triazole 2,4,6-trinitroresorcinic acid 14.5 ml of 9895 Mona is subject to utilization. a) obtaining triaminoguanidinium chloride.

14.5 ml of 9895 MoNu are poured into the reactor, equipped with a mechanical stirrer, a drip funnel, and placed in a bath with a coolant, then 1 bml of water is added drop by drop. When stirring, add 15 ml of 3495 HC1 from a dropper so that the temperature does not exceed 802С. Then add 9.5 g of dicyandiamide (DOCDA).

The reaction mass is heated to 1-85-902С7 and kept at this temperature and movement for 1 hour, without stirring - 2 hours.

The reaction mass is cooled to room temperature. The precipitate of the precipitated product is filtered, 65 squeezed, washed with ice water (2x3 Oml), dried in air. Output 14.1g (88905). PTld-237-23996. b) receiving salt

14.1 g of triaminoguanidinium chloride is cyclized under conditions similar to those given in example 1, and 14.8 g (73965) of 5-methyl-4-amino-3-hydrazino-1,2,4-triazole dihydrochloride are obtained. The resulting salt is dissolved in 25 mL of hot water and added with stirring to the sodium styphnate solution, which is prepared from 18 g of styphnic

ACIDS, bg Mahon and 100 ml of hot water. The solution is cooled, kept at room temperature for an hour, the precipitate formed is filtered off, washed with ice water, dried in air. Yield of 2,4,6-trinitroresorcinic acid 5-methyl-4-amino-3-hydrazino-1,2,4-triazole 19.8 g (72905).

Similarly, picric acid 5-methyl-4-amino-3-hydrazino-1,2,4-triazole, Tpdl--118-12596, is obtained

3-methylpicric acid 5-methyl-4-amino-3-hydrazino-1,2,4-triazole. 70 Example 5

Utilization of hydrazine and MMG to obtain a mixture of (4-methylammonium-1,2,4-triazolyl-3)-hydrazinium diperchlorate and 3(1-methylhydrazinium)-(1,2,4-triazolyl-4)-ammonium diperchlorate.

16.3 g of 9895 M»Nad 1) obtained from a mixture of salts (1-(2,6-dichlorobenzylideneamino)-2-methyl-2,3-diaminoguanidinium chloride and 75. 1-(2,6-dichlorobenzylideneamino)-2- methylamino-3-aminoguanidinium chloride.

To a solution of 1 bml of 9895 M2Nai in 500 ml of water, with external cooling to (-0-109С), 18.8 g of С52 are added for 30 minutes. A precipitate of hydrazinium dithiocarbazinate is formed, which is filtered off and squeezed on a filter.

The product is dissolved in the minimally necessary amount of hot water and, with intensive stirring, the prepared suspension of bbg RB(OH)" is added to bOml of water, after which the reaction mass is heated for another 20 minutes. The precipitate Pb5 2o is filtered, washed with hot water, the filtrate is cooled to room temperature. The formed precipitate of thiocarbonohydrazide is filtered, washed with cold water, dried in air. Output 21.2g (8196). Tdd-168-169296 (with declaration) (with НХО).

The obtained thiocarbohydrazide is added to 100 ml of absolute ethanol, 29.0 g of CHCl is added, heated and refluxed for 5 hours, then cooled to room temperature. Precipitate

The resulting 3-mmethylisothiocarbohydrazide iodide is filtered off, washed with cold alcohol, and air-dried. Output 4Ω (80965).

The obtained salt is suspended in 150 ml of hot ethanol and 28.0 g of 2,6-dichlorobenzaldehyde is added. The reaction mass is refluxed for 4 hours, cooled to room temperature. The precipitate of 1-22,6-dichlorobenzylidene)-8-methylisothiocarbonohydrazide iodide is filtered off, washed with cold alcohol, dried in air. Output 41.4g (9295).

The obtained salt is suspended in 150 ml of ethanol under heating and 7.42 g of MMG is added. oh

The reaction mass is maintained at 60-802C in a flask with a reflux condenser until the formation of methyl mercaptan stops. with

The reaction mass is neutralized with 25956 MNuz, partially evaporated under vacuum on a rotary evaporator with solvent distillation, the residue is acidified with 14 ml of concentrated HCl, cooled, the precipitate is filtered off, washed with cold ethanol, dried in air. Yield of a mixture of salts (1-(-2,6-dichlorobenzylideneamino)-2-methyl-2,3-diaminoguanidinium chloride and 1-2,6-dichlorobenzylideneamino)-2-methylamino-3-aminoguanidinium chloride) 33.2g (7290) . "2) production of chloride salts.

The resulting mixture of salts is suspended in 7 Oml of 8595 NCOOH and refluxed for - s 2 hours. The reaction mass is evaporated under vacuum on a rotary evaporator with NCOOH residue, the rest is dissolved in 100 ml of carrier medium, refluxed for 0.5 hours. A mixture of salts is obtained (if necessary, 3-(1-methylhydrazino)-4-(2,6-dichlorobenzylideneamino)-1,2,4-triazole hydrochloride and -- 3-(2,6-dichlorobenzylidenehydrazino) can be isolated from the mixture by chromatographic method -4-methylamino-1,2,4-triazole hydrochloride, Trpl-205-2072C), which is then boiled for 2 hours, cooled, extracted with hot benzene, the extract is separated, the aqueous solution is acidified with 50 ml of concentrated HCl, boiled with by distillation of a portion of the liquid phase for 2 hours, extracted again with benzene, extract 1 is separated. The aqueous solution is evaporated under vacuum on a rotary evaporator, the thick residue is dissolved in

Ge» 20 of the minimum required amount of warm water. A solution of 40 g of RB(SiO4)2"ZH"O in 7 Oml of water is added to the solution, the reaction mass is cooled, the formed PBSI precipitate is filtered off, washed with ice water, and the combined filtrates are concentrated by evaporation under vacuum or in a water bath, 37 g of 7595 solution of a mixture of (4-methylammonium-1,2,4-triazolyl-3)-hydrazinium diperchlorate and

C(1-methylhydrazinium)-(1,2,4-triazolyl-4)-ammonium diperchlorate. 59 The above examples of the implementation of a useful model clearly indicate the possibility of utilization of non-standard liquid rocket fuels based on hydrazine and its M-alkyl and M,M-dialkyl derivatives with obtaining energy-intensive salts of some 1, 2, 4-triazole derivatives. The latter can be used as components of industrial BPs (including aqueous and emulsion BPs) and components of solid and polymolecular rocket fuels.

Claims (1)

The formula of the invention 1. The method of disposal of hydrazine-containing liquid rocket propellants (LPP), which includes their chemical modification by interaction with a chemical reagent (acid) in a solvent medium (lower aliphatic alcohol), because it differs in that the chemical modification is carried out in three stages, hydrazine is also disposed of, monoalkylhydrazine, M,M-dialkylhydrazines and aerosin-50 (a mixture of equal mass parts of asymmetric dimethylhydrazine (NDMH) and MoH"), at the first stage, an intermediate of compound A of the general formula is obtained: VMS(MeMeV 2"(NH)a or VgMS(MeMeV HMeMASNAGU (NH) a, where B, KE! - H, CH, CoHrB; B? - H, AK, MAV; AK - alkyl C4-Su; НХ - HnNa), 1/2H550.4, NOBOZAIK, NOBO»5AG, a-o0,1,2; e Ag - ОВ Н, СНО, СНОМ, Най, Но, and in the second stage the obtained intermediate is cyclized to obtain compounds B of the general formula: Кк м шо М--м Ж me mn ME 5. ИЧ " E 1 p (NAp m k | " (NAPu- VAYAE « (NAT, | (NAPi- VAVE! (NA, 1 Me! ME e Kk dv IM A- mA A-kmet o ih ' MEM e5 MI e5 M | "« (NAt - NABEZ v (NA t t (NApi - VABE? v (NA p' ' MAE so MAE "so de Ap' - SI, Vg, I, 1/250), NBZO,, NoRO" ; 6vB-0,1,2, IC) at the third stage, by the interaction of compounds B with salts of MAp', the final salts of 1,2,4-triazole derivatives with the general formula are obtained: (VAZE a«(НАп с, (VAZE )а" NAp s, (VAZE?)a"(NAp s, (VAZEZ)(NAp b, - de Ap'- MO", SIO/U S(MO2)37, S(SM)37, MSH(MO2)27, M37 , (МО2)»СН", 1/2ИС(МО2)2157, (02М)ДСН-С МО 2)», МО, МО МО Сн " shi s ORK - 00M and o 05M o-, 0-, bom og, "with sp p o (8) o sleep 02 no 00? y - so o-y. U o oz v she MN i m-n -- ' y M s, t sy r ny di o pd y - bu MO M M "m? o them o syu" THEM what I M g, o-- Mo 0000 la SNIMOg» y, s n - О2ММНОСНоСНоМ МО», О2MMНСНоМ МО», 1/2СНо(М'МО2)», В'М' MO"; p-125a: 1,2, 60 where M' - ii, Ma, K, МН,, 1/2Са, 1/2Ва, 1/2Ма, 1/2Р5, 1/2На, Av. 2. The method according to claim 1, which differs in that at the first stage, the utilized hydrazine-containing PRP is treated sequentially with RG reagents, then, if necessary, RO or RI(OH)", then, if necessary, AGSNO and AIiKH with subsequent treatment with hydrazine-containing PRP or amine AIKMN" or MN" with isolation of intermediate A by known methods, and the reagent RG belongs to the following series: SZZ", SZSI", AIKMO5, NOMSM, ENMSM, KoMeSM, because NoMS(MN)MNSM, Naism, NZSM or M'ZSM , (Н»Мм)бС - МН, where Na! - SI, Vg, I; M'- Ma, Gi, K, 1/2Sa, 1/2Ba, 1/2Ma9. C. The method according to claim 1, which differs in that, in the second stage, intermediate A is cyclized by sequential treatment with a carboxylic acid of the general formula B'COOH at a temperature of 50-130 °C for 0.3-20.0 hours and treatment with a solution of NAp in aqueous , in a water-alcohol environment at a temperature of 80-120 °C for 0.3-6.0 hours with the separation of by-products by known methods and obtaining salts in the form of solutions and/or in a solid state after evaporation of excess solvent. 4. The method according to claim 1, which differs in that at the third stage of the interaction of compounds B with salts MAp! or with acids NAp!' carried out in an aqueous, aqueous-organic or organic solvent at a temperature of -10 70-50 for 0.1-2.0 hours, and the final salts of 1,2,4-triazole derivatives are obtained in the form of concentrated solutions and/or in a solid state after evaporation of solvents, and alcohols AIKON, diethyl ether, dimethylformamide, dimethylsulfoxide, acetonitrile and/or their mixtures are used as organic solvents. 5. The method according to claims 1, 2, 3, 4, which differs in that water and/or organic solvents, which are distilled off during the concentration of solutions of substances A, B and terminal salts of 1,2,4-triazole derivatives, are used at the next stage synthesis of salts. 6. The method according to claims 1, 2, which differs in that the gases formed during the preparation of substances A and/or B are washed with solutions of NU acids, where U is MOz, SIOH, C(MO»)z, ORK, M( MO"))" with obtaining the corresponding salts. 7. The method according to claim 1, which differs in that mixtures of salts of 1,2,4-triazole derivatives are obtained. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2006, M 4, 15.04.2006. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. - so (Se) IS) so h- - with . and? - (95) 1 b 50 syu» with 60 b5