PL102660B1 - THE METHOD OF THE PRODUCTION OF THIOPHOSPHATES - Google Patents

Description

The patent description was published: 29/09/1979 102660 Int. CL2 C07F 9 / | fe5 Inventor Patent holder: The Dow Chemical Company, Midland (United States of America) Method for the production of thiophosphates and The invention relates to a manufacturing process thiophosphates.

O-Pyridyl Phosphates and Phosphates. Phosphates described in the United States patent of Aimeryka No. 3 244 566. The above relations are especially useful as insecticides and means destroy living systems. Sa. is a relationship with a pattern r 1, in which E is and a group of chloro-pyridines- low, Z is oxygen or sulfur and R 'is not depending on each other, they mean the lower alkyloxy group low, amino, or lower alkyl or less.

It describes various manufacturing methods as above higher relationships, but the advantage of them lies in the reaction of chlorophosphate or oMophothiophosphate o formula 2 from a metal salt of a halopyridinol alkali of the formula R, O-alkali metal or amine (tertiary with the formula R-OH- - tertiary amine.

In the described process, the process is carried out in Obo a suitable organic solvent; under condition waterless canes. In any of the ways described as an intermediate, an aluminum metal chloride is formed calcined lub hydrochloride of tertiary ami¬ ny, which are removed by desiccation.

In known processes as zalpew- catalysts Very fast reactions have been used ny. However, the product was obtained in a low yield wear, contaminated with a large amount of u- sides that had to be removed. Therefore the purification step of the product was difficult.

Quaternary salts can also be sitos are themselves important to catalyze the reaction. In this case in this case, you get a completely pure product. Jed Nakze, hence the low speed catalyst concentration the reaction is generally too small in relation to the shaft industrial markets. At a higher concentration of the catalyst, the rate of reaction increased but increased difficulties are associated with the removal of the catalyst from the end product.

It was surprisingly found that the mixture was quaternary ammonium salts and various amines tertiary reaction speeds up the course of the reaction to at least as fast as observed when amines alone are used, moreover, then the efficiency is increased and the content is reduced " undesirable by-products.

The invention relates to a process for the preparation of thiophene of phosphates of the general formula 3, wherein Rt is an alkyl group, R, aU, carboxy or phe- nylon and R is hexagonal, carbocyclic- an aromatic ring or heterocyclic ring, e.g. having 0 ^ 3 substituents such as group Filter, cyano, chloro, alkyl wa, alkoxy * alkylthio or alkylsHfinyl- but it can only be among the substituents dine nitro, alkylthio or alkylsiline group nylon and the alkyl and alkoxy groups contain 1-4 atoms are defined as being in the group of the formula: 4, in which R x and R2 have the abovementioned symbols connection, consisting in the fact that the compound 102 660 102 660 3, ¦-. ; s. phosphic of general formula 5, where Rx and R2 have the meanings given above, subject to the re of an action with a salt of the formula RhOM, wherein R is v with the exception of the group represented by the formula below 4 and M is an alkali metal atom or, 5 where R is the group of formula 4, with soda of the formula MO-C6H4-S-CeH4-OM, in which M is alom, an alkali metal, in liquid in the reaction environment and in the presence of a catalyst quaternary ammonium or phosphorus 10 salts with at least 10 atoms carbon and being soluble in the environment the reaction efficiency is at least 1% by weight, and tertiary, unobstructed ethe organic nucleophilic amines. 15 fóoduktaimi of fundamental importance are a relationship ki, wherein R is a group of formula 6, 7, 8 or fl where n is zero or has the value% 1-3 and X represents the group of mithrov, cyanbwa, aitom halogen (fluorine, chlorine, bromine or iodine), group 20 alkyl, alkoxy, alkylthio or alkylsul- phinyl, with the proviso that the group R cannot be substituted with more than one nitro group, alkylthio or alkylsulfinyl. Alkyl groups and alkoxy groups contain in each case 25 l> - ^ 4 carbon atoms dust and butyl).

When using the above complexes catalysts, compounds of formula III are obtained with satisfactory in industrial conditions glass panes - 8 (j bone of reaction and excellent efficiency and cleanliness.

The use of these complex catalysts provides thus improving the known process.

Virtually every union in a known group quaternary ammonium and phosphonium salts 35 can be used in the manner according to the invention zku. Quaternary ammonium salts are suitable and phosphonium, which are soluble in liquid reaction medium at a temperature of 25 ° C, of at least 1% by weight and containing - 40 eggs in the molecule at least about 10, preferably about 12-31 carbon atoms. These salts have a general purpose the formula RtlR / R / R / Q + A ~, wherein R /, R2 ', R3' and R4 'is a hydrocarbyl radical, for example an alkyl radical s, aryl, alkylaryl, arylalkyl, cyclo- alkyl and the like and Q + is quaternary nitrogen or phosphorus aitome. In addition, R / and R2 'may . create a total of 5 or a hexagonal breast a heterocyclic shadow having at least one den is a quaternary nitrogen, oxygen or sulfur atom, gQ not adjacent to the previous heteroatom.

In a typical case, R 1, B.2, R 3 'and "T" are Czaja groups containing from 1 to about 12 aJtoms coal. A- is inert under the reaction conditions, an obliterating anion that may turn into a 55 dependence on need. Chlorine anions are preferred and goal but also other such as fluoride, iodide, bisulfate, super chlorate, nitrate, acetate, p-toluenesulfonate, benzo esan and (similar eo The following relationships may serve as an example: tetraalkylammonium salts such as chlorides, bromine ki, bisulfates, p-tolnenesulfonates and others tetra-n-butylammonium, tetrahexylammonium, tri-n-butylmethylammonium, cetyltrimethylammonium 65 ; 4 ¦!; ¦ mono, trioctylmethylammonium and tridecyl- methylammonium; aralkylammonium salts such such as chlorides, bromides and other tetrabenzyl ammonium. benzyltrimethylalmonium, toenzyltriethylammonium new, benzyltributylammonium and phenetic tyloammonium; arylammonium salts such as fluoro oride, chloride lulb bromide triphenylmethylammonium- Y, N, N, NH-trimethylaniline bromide, hydrogen N, N-dimethyl-iN-methylaniline sulfate, chloride- trimethylnaphthylammonium chloride or p-methylphenyltrimethylammonium sulfonate, etc. ne; five- and six-membered heterocyclic compounds ne containing at least one quaternary a nitrogen atom in the foam, such as chloride or N-methylpyridinium methyl sulfate, N-he- iodide xylpyridinium chloride (4H-pyridyl) H -trimefcyl- ammonium, l-methyl-l-azadi bromide; Cyclo (2.2.1) < heptane, N, N, dibutylmorpholine chloride, chlorine N-ethylthiazoilyl recycle, N-butylpyrrolic chloride and others, and the corresponding phosphonium salts and others kind relationships.

Ammonium salts are presently preferred in proportion to phosphoniums for reasons of price and access trade. The most preferred catalysts rami sa ibenzyltrimethylammonium salts, benzyl- triethylammonium, tetra-n-butylammonium ora * tri-n-fcutylmethylammonium.

The quaternary ammonium and phosphonium salt stack they are eaten in small but catalytic amounts. By cladowo, the right amount is from about 04 to about 20 mole percent per mole of substrate and about 20 mole percent Preferably from about 0.5 to about 10 mole percent. Jateo amines are used without interfering with ethe rically, nucleophilic tertiary organic amines nothing. Suitable for the described purposes of arniin should react with cMorothiophosphates and pheny- lochloTothiophosphonates, create as reactive- transition compounds, molar adducts in relation 1: 1. Such adducts can be identified using. one of the well-known analytical techniques, e.g. ultraviolet trometry.

In practice, however, in most cases you can use the following procedure for tertiary amine performance testing f as a co-catalyst in the described process. Check the demand is that equimolar Quantities tertiary amine and chlorothiophosphate or phe- The nylchlorothiophosphonate is stirred into ethyl ether at room temperature, and it is assessed whether does or does not form an insoluble complex in the ether.

Suitable in almost all cases as catalysts for the tertiary amine reaction in question The government forms an ether-insoluble complex xs with the phosphorus compounds in question, after thirteen minutes of mixing. More effective Amines acting as catalysts form insoluble matter ether-soluble complexes almost immediately cities after mixing. For suitable thirds carcinomas include e.g. 1,4-diaxial 1cyclo- <2,2,2) acane, diazoles such as imidazole, pyrazole or them 1-alkyl derivatives; aliphatic tricarbonate amines— hydrogen such as trimethylamine, ethyldibu methylamine, butyldimethylamine, N, N, N ', NV - C-tetromethylethylenediamine and the like; aMfa — 102,660 "tic heterocyclic amines such as 1-aza-dio cyclo (2,2,2,) octane, 1Hmeltyl-2-imidazoline, 1-aneth- lojpirolidyoa and the like; and mixed alpha-amines no-aromatics such as 4- (N, NH-dimethylami- no) -pyridiha, 4- (N-pyrrolidine) pyridine, phenyldi- methylamine and the like, and others like, no sterically hindered, nucleotrophic tertiary organic amines.

Tertiary amines are used here process in small but kaitaiic amounts. By A suitable amount is from about 0.25 to about 20 mole percent is a mole of substrate and about 20 mole percent Preferably from about 0.5 to about 10 mole percent.

Examples of suitable combinations of quaternary standard ammonium salts and tertiary amines are as follows: chloride, benzyltriethylphosphate nium and trimethylamine, benzyltriethyl bromide ammonium and trimethylamine, bisulfate, tetras -n-tetylammonium and 1-azadbicycle (2,2,2) ocitane, tri-n-buftylammonium bromide and 1'-methylpyrrolidides- Na, Ittriphenylmethylphosphonium chloride and 4- -dimethylamino) -pyridine, tetra-n-butyracetate- phosphonium and pyridine, 2,4-dichlorobene chloride ethyltrimethylammonium and 3-or 4-picoline, chlorine tridecylmethylammonium and 4- (N, N-dimeth- loamino> pyridine, octadecyltrimethylbromide ammonium and trimethylamine, chloride benzyltrium- ethylammonium and 1-methylimidazole, chloride ibenzy- triethylammonium and 1,4-dio-bicyclo (2.2r2) ok- tano-triethylene divalimine and others.

Alkali metal salts of phenols, pyridinols and pyrimidinols are known group of compounds to correspond giving the formulas R-C-M + and M + 0 - C6H4-S-C6H4- -0-M +, wherein R is as defined above and M is an alkali metal, for example, Hitu, so high or preferably sodium or potassium and most preferably preferably sodium.

Ghlo-rotiophosphates 0,0H-dialkyl- and phenylchlo- O-alkyl thiophosphonates are ipodoibble to the known groups of compounds with formulas 10 and dli, in which Ri and R2 are, independently of each other, a lower group alkyl, preferably methyl or ethyl.

It is obvious that the various phosphorothioates and phenyl Thiophosphonates are prepared using various compositions combinations of the outputs discussed above out. Tables 1 and 2 show a list of representatives positive suitable starting compounds and their various combinations.

The reaction proceeds with a satisfactory speed in temperature from about 0 ° C to about 100 ° C, the best however, drink in a temperature range of about 40 ° C up to about 60 ° C. The pressure is not a flange size the process is generally carried out under pressure atmospheric or elevated temperatures, in particular dependence on convenience. Under the above conditions, re-j action takes place within 8 hours and usually 0.25-5 hours is sufficient to complete complete reaction Oppressive solvents can be, for example, vesicles hydrocarbons such as benzene, toluene, xylene and others halogenated hydrocarbons such as methyl chloride nu, chloroform, carbon tetrachloride, tetrachloro- ^ Tylen and others. Two-phase ones are suitable a mixture of water and immiscible with water inert organic solvent, for example mixed Table 1 Scheme 1 40 45 ? ° No 1 2 3 4 * 6 7 8 9 11 12 13 14 1 16 Ri 1 * CH3 C * H5 Q, H5 CH, __ C2H5 CH, CH3 C2H5 CH ,.

CH3 CH3 C2H5 and C2H5 C2H5 C2Hf CH3 * Rom CH, C * H5 C2H5 CH3 C * H5 CH3 CH3 C * H5 CH3 CH3 CH3 CjHg C2H5 CA CaHs CH3 and R formula li2 pattern 12 pattern 13 pattern 14 pattern 15 pattern 16 pattern 17 pattern 18 pattern 19 pattern 20 pattern 20 pattern 21 pattern 22 pattern 23 pattern 24 pattern 25 1 M On On On At 1 K. On On On K. K. On On On K. On K. " No 17 18 19 1 21 Table 2 Scheme 2 Ri CH3 C2H5 CzHs CH3 C2H5 R pattern 26 pattern 18 pattern 25 pattern 27 pattern 27 * M On K- On On On 65 a hydrocarbon or a halogenated hydrocarbon gas and water. A preferred soluble is chlorinated methylene rec or a mixture thereof with water.

The reactions are carried out in an alkaline environment, which is obtained with sodium hydroxide of any other principle or system him buffering.

It is desirable to agitate the reaction mixture especially if the process is carried out on a Wednesday in a two-phase solution, e.g. in a chloride mixture methylene and water.

The invention is illustrated by examples.

Pnz-example I. Reactions between 9.5 g and (0.05 mol) O, O-diethyl chlorothiophosphate and 12.0 g. 0.05 m Ia) sodium 3,5,6-trichloro-2H-pyrryldinolate, pro charged in a mixture of methylene chloride and water, a mixture containing 3% mol is catalyzed in benzyltrimethylammonium chloride and 1-2%; molar amounts of one of the following amines: clo (2,2,2) olctane, trimethylamine, N-methylpyrrolidine- na and 4- (NJT-dimethylamino> pyridine.

The reactions are carried out for 1-2 hours at at boiling point to obtain phosphorothioate O, O-diethyl-O-3,5,6-tri-chloropyridyl-2 ex yield over 9 (P / o of theoretical yield. Pro the product separates, separating the organic phase, washing it three times with water and distilling it fractionated to remove the solvent nika. 102 660 Example II. The procedure is repeated sane in example I, using as catalysts combinations of compounds given in Table 3. 8 coolers and a drip tray, place 30 ml of chlorine towards methylene. 74 ml of water, 3.5 g of sodium chloride, 0.43 g of sodium hydroxide, 0.78 g of boron acid Table 3 Sample no 1 2 3 4 6 7 8 9 salt Type BTEAC *) BTEAC BTEAC BTEAC BTEAC BTEAC BTEAC BTEAC BTEAC TBAa **) mole% 1 2 1 Amine Type 4-picoline Chimukiidin N, N-dimethylaniline N-methylmorpholine Cziteroimethylethylene- diamine Benzyldiephthylamine 4-i (dimethylamino) - pyridine Trimethylamine Troymethylamine 4- pyridine mole% 2 2 1 Time h. 3 1.1 9.5 9.0 3.3 7.0 1.0 1.0 , 5 0.7 x Performance in% 88.6 94.6 90.2 90.8 91.0 69.2 89.2 94.6 90.2 99.7 | *) benzyltriethylammonium chloride **) tetrabitylammonium bromide Ponzyklad III. Preparation of thiophosphate 0,0-dimethyl-0-3,5,6- (trichloropyridyl-i2.

In a three-necked flask equipped with a stirrer, coolers, and a drip pan, place 30 ml of chlorine methylene, 74 ml of water, 3.3 g of sodium chloride, 0.38 g of sodium hydroxide, 0.7 g of boron acid 0.13 g (0.56 mmoles) of benzyl triethyl chloride laammonium, 0.05 g (0.56 mmol) of 1-imethylim- dazol and Ii2.5 g, (36 mmol) 3,5,6-trichiloro-2- -sodium pyridinolate. Everything is mixed, warm wa up to 35 ° C, add in one minutes 9.03 g (36.3 mmol) of chlorothiophosphoram 0.0-dimethyl DMPCT and heated to application (42 ° C) within 1.5 hours. Organic layer some are separated, washed with 100 ml of water and then washed with water stepwise removes the chloride (methylene on a rotary evaporator towa. After cooling down in the ice bath it is replaced 17.3 g (93.7%) 0.0-dimethyl-0-3 thiophosphate, , 6-trichloropyridyl-2 in the form of white crystals easels.

The following is performed in a similar manner series of experiments listed in Table 4. 0.14 g (0.6 mmol) of petroleum chloride of lammonium, 0.04 g (0.45 mmol) of 1-methylimi- dazol and 13.2 g (60 mmol) of 3,5,6-trichoro-2- -sodium pyridinolate. Everything is stirred and heated wa to 35 ° C, then added w within one minute 11.3 g (60 millimoles) cMorothio- O, O-diethyl phosphate DEPCT and heated to boiling point (42 ° C) for 3.9 hours. War¬ The organic matter is separated and washed with 100 ml of water dy and methylene chloride is evaporated in an evaporator rotary. After cooling in an ice bath, it was There is 19.41 g (92.43 D / o) of white crystalline 99.5% pure product.

The following is performed in a similar manner the series of experiments listed in Table 5.

Chloride benzyl trio ethylammonium mole% 1 0.75 0.50 0.75 - 1 Table 4 1-methylimi- dazol mole% 1 0.75 0.50 0.50 1 - Time h. 1.6 3.8 4.5 3.1 3.5 23.0 Performance*; % ^ 93.7 94.9 94.6 91.7 36.5 40.0 *) after isolation Example IV. -Thiophosphate production 0.0- Hdiwuetya-10-3,5,6-trichloro-pyridyl-2.

In a three-necked flask equipped with a stirrer, 45 50 55 60 65 Petroleum chloride zyltriethyl ammonium mole% 1 1. 0.75 0.75 0.50 Tabl mole% 1-methylimi- dazol 1 0.75 0.75 0.50 0.50 Imidazole Pyrazole and ca 5 Time hours 2.2 3.9 3.6 , 1 3.8 7.1 28 Performance*) 97.1 92.4 94.0 89.0 95.7 94.6 88.5 Clean tosc % 98.2 99.5 98.0 97.1 97.7 - - *) after isolation Example V. Repeating previously described the procedure is carried out as follows: benefits. In any case, as a catalyst use a mixture of benzyltriethyl chloride ammonium and 1H-methylimidazole. In trials 1-5 0.75 mol% of each catalyst is used in relation to the starting compounds, nato - 102 660 9 Instead, in Run 6, 1.0 mole percent of each catalyst Torah. In trials 1–3 the stacking levels are similar to those in (examples HI and IV boric acid, while v in trials 4-6, this relationship is not used. Results The experiments are presented in Table 6.

Example VI. Production of thiophosphate 0.0- J-dimethyl-0-3,5,6-trichloropyridyl-2.

To a mixture of 13.2 g (0.06 mol) 3,5,6-trichloro Sodium -2-pyridinoleate, 30 ml of methyl chloride nu, 74 ml of water, containing 1 mole% trieth- lenediamines; and a buffer containing hydroxide sodium and sodium borate are added dropwise during the mixture 11.3 g (0.06 mol) of 0.0-di-chlorothiophosphate mercury. Everything is mixed for 1.5 hours in temperature of 42 ° C, then cooled to a temperature of room temperature and the organic phase is separated.

The organic layer is washed once 30 ml of water and the solvent is evaporated off under reduced pressure. The product is obtained with a yield of 97%, assuming 100% conversion ny starting relationships. The purity of the product is excellent and amounts to about 99%.

Example VII. The procedure is repeated with of the previous example, using the same re¬ reaction agents and conditions, except catalysts and reaction time. The results are shown in the table below blocks 7 and 7a.

Blackboard! 7 No trials 1 2 Co-catalysts CeHgCH2-iN + - (CH3) 3Cl- Three yelenidwoimma pattern 40 Triethylene divalimine % pier out 2 2 1 1 Time reaction at 54 17.75 % output nosc 94 97 Example VIII.

Table 7a 1 Sample No. | 1 2 Reagents DEPCT + pattern 41 DEPCT +. pattern 43 Product | model 42 1 pattern 44 | DEPCT '* - 0,0-diethyl chlorotidophosphate. and and pyrimidonol, taking In a series of experiments, the procedure and are used reaction conditions almost the same as described in Example VI, with the proviso that the reaction time is 3- - 4 hours and not added to the reaction mixture of boric acid. Moreover, less is used higher amount of catalyst, namely 0.75 mol% it is triethylenediamine and 0.75 mole% chloride benzyltriethylalmonium. In test 1, the product is eaten with a yield of 92.1% and in trial 2 with a yield of 93.1%.

Claims (24)

1. Claims / Patent 1. A method for the preparation of thiophosphates of general formula (III), in which R 1 represents an alkyl group, R 2 represents an alkoxy or phenyl group, and R represents a hexagonal, carbocyclic or heterocyclic aromatic radical containing 0-3 substituents such as the nitro group , cyano, halogen, alkyl, alkoxy, adkylthio or alkylsulfinyl groups, provided that there may be no more than one nitro, alkylthio or alkylsulrinyl group among the substituents, and the alkyl and alkoxy groups contain 1-4 carbon atoms , characterized in that a chlorophosphorus compound of general formula 5, in which R1 and R2 are as defined above, is reacted with a salt of formula R-OM in which R is as defined above and M is an alkali metal atom, in the liquid reaction medium and in the presence of quaternary catalysts) 1 ici: t) L \ sr) sodium s 40 50 55 60 Sample number 1 2 3 4 ¦ 5 6 DMPCT reactants - formula 28 C8H54P (S) + formula 30 - C1 DMPTC + and formula 32 DMPCT + formula 34 DEPCT -h formula 36 DMPCT + • formula 38 Table 6 Product formula i29 formula 31 formula 33 Formula 3i5 formula 37 formula 39 Reaction time h. 2.5 2.5 3 7 6 1% conversion 100 78.1 100 not measured not measured 100 *) the conversion of sodium phenols derivatives was calculated on the basis of the solution, pyrite 100% conversion for trials 4 and 5 ** percentage yield was calculated on the basis of transformation stage Sample No. 1 2 3 4 5 6 DMPCT reagents - formula 28 C8H54P (S) + formula 30 -Cl DMPTC + and formula 32 DMPCT + formula 34 DEPCT -h formula 36 DMPCT + • formula 38 Product formula i29 formula 31 formula 33 Formula 3i5 Formula 37 Formula 39 Response time h. 2.5 2.5 3 7 6 1% conversion *) 100 78.1 100 not measured not measured 100 Efficiency ** 95.4 95.4 approx. 100 82 86 92 Product description red oil white brown sediment liquid liquid 1 nD 1.5131 liquid 1.4953 nD 1.5587 vol 115 ° C / / 1.5 mmHg | of p102 660 11 grade p102 660 11 anhydrous or phosphonium salts having at least 10 carbon atoms and having a solubility of at least 1f / t by weight in the reaction environment and a tertiary, steric free, organic amine. 2. Wrong way according to sitrz. The method of claim 1, characterized in that the quaternary ammonium or phosphonium salt and the tertiary amine are used in an amount of 0.1 to 200% moles with respect to the excipients used. 3. The method according to p. The method of claim 1, wherein the quaternary ammonium or phosphonium salt and the tertiary ammonium salt are used in an amount of 0.5-105% mol relative to the starting compounds used. 4. The method according to p. The process of claim 1, wherein the reactions are carried out at (temperature 0-100 ° C. 5. The method according to p. The process of claim 4, wherein the reactions are carried out at a temperature of 40 ° C to 0 ° C. 6. The method according to p. The process of claim 1, wherein the liquid reaction medium is hydrogen or a halogenated hydrocarbon. 7. The method according to p. The process of claim 1, wherein the liquid reaction medium is a mixture of an inert, water-immiscible organic solvent and water. &. The method according to p. The process of claim 1, wherein methylene chloride is used as the organic solvent. 9. The method according to claim 1, characterized in that a quaternary ammonium or phosphonium salt having 12-31 carbon atoms is used. 10. Way according to satr. The process of claim 1, wherein the quaternary ammonium sodium is benzyltrimethylampnium chloride, benzyltriethylammonium chloride, tetra-n-butylammonium bromide or tetra-n-butylammonium chloride. 11. The method according to p. A process as claimed in claim 1, characterized in that the tertiary amine is / 1-azadibyclo (2.2.2) octane, trimethylamine, N-methylpyrrole, 4-ne, quinuclidine, tributylamine, N, N-dimethylaniline, N-methylmonfoline, tetramethylethylene diamine, benzyl dimeptylamine, triphenylamine, 1,4-4 diadicyclo <2.2.2) octane or 1-meltylimidazole. 12. Method according to zalstrz. A compound according to claim 1, wherein the starting compound is a compound of the formula R-OM, in which R is a group of formula 6, 7, 8 or 9, in which n is zero or has a value of 1-3 and X is cyano, filter, halogen, allkyl, alkoxy, aOkylthio or alkylsulfinyl groups, provided that the R group may not be substituted by more than one nitro, alkiiotio or alkylsulfinyl group, and the alkyl and alkoxy groups contain 1- 4 carbon atoms and M is alkaline mefcal. 13. The method according to p. A compound according to claim 1, characterized in that the starting compound is a compound of the formula R, OM, in which R is 3,5,6-trichloro-2-iridyl-2 and M is an alkali metal. 14. A process for the preparation of thiophosphates of the general formula 3, in which R 1 is an alkyl group, R 2 is an alkoxy or phenyl group and R is a group of the formula 4, in which R 1 and R 2 are as defined above, characterized in that The chloraphosphorus compound of general formula V in which R1 and R2 are as defined above is reacted with a salt of formula MO-C6H4-S--iCfH4-OM, in which M is an alkali metal atom, in a liquid reaction medium. and the presence as catalysts of quaternary ammonium or phosphonium salts having at least 10 carbon atoms and having a solubility of at least 1% by weight in the reaction medium and a tertiary steric free, nucleophilic organic amine. 15. The method according to p. The method of claim 1, wherein the quaternary ammonium or phosphonium salt and the tertiary amine are used in an amount of 0.1-20% mol on the starting materials used. 16. Way according to zasitrz. The method of claim 14, characterized in that the quaternary ammonium or phosphonium salt and the tertiary amine are used in an amount of 0.5-10% molar with respect to the starting compounds used. 17. The method according to p. The process of claim 14, wherein the reactions are carried out at 0-10 ° C. IB. The method according to p. 17, characterized in that the reactions are carried out at 40-60 ° C. 19. The method according to claim The process as claimed in claim 14, wherein the liquid reaction medium is hydrogen or hydrocarbon hydrogen. 20. The method according to claim The process of claim 14, wherein the liquid reaction medium is a mixture of an inert, water-immiscible organic solvent and water. 21. The method according to p. The process of claim 20, wherein the organic solvent is methylene chloride. 22. Way according to zasitrz. The process of claim 14, wherein a quaternary ammonium or phosphonium salt having 12-31 carbon atoms is used. 23. The method according to claim 14. The method of claim 14, characterized in that the quaternary ammonium salt is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetra-n-buitylammonium bromide or oztero-n-tofutylammonium chloride, 24. The method according to claim 14. A process as claimed in claim 14, characterized in that the tertiary amine is 1-azadibyclo (2 ^ y2) octane, trimethylamine, N-methylSLpyrrolidine, 4- (N, N-diniethylamino) - ^) iridine, 4-nipicycloic, quinuclidine , trybutyylamine, N, N-dimethylolylamine, N-methylmorphofline, tetramethylthyleriodiamine, benzyldimethylamine, triphenylamine, 1,4-dibutyyl (2,2,2) octane or 1-methylimidazole. 15 20 25 30 35 40 45 50 55 102 660 R-O-P-R 'model 1 Cl— P —R' R 'MODEL 2 R9-0-P-Cl + R-0 M -> R-0-P-0-R. Rr0 SCHEME 1 0-R <ROP-Ro I O-Rt WZCR 3 r2-po-c6h4-s-c6h4- O-Rt WZdR k Cl - P - R2 I 0 — R-, MODEL 5 (X) n (X ) n Formula 6 N Formula 7 Formula 12 Formula 13 Cl Cl Formula 16 NO- Formula 17 ^ K -lX) n N Formula 8 Formula 9 / Vno- Formula 18 CH, NO- Formula 19- S R2-0-P -Cl R, -0 10 C6H5-P-Cl RpO Formula 11 hQ-s-ch3 CH3 Formula 20 O -Q ^ CH, Formula 21102 660 Cl Cl NaO - @ - Br- »C6H5-P (S) -0- ^ -Br Cl Cl Formula 30 Formula 31 NaO h (oVno2 -> (ch3o + 2p (s) -o ^ OV CH, N02 CH, Formula 32 VJzi-- 33 NaO - ^ O) -> (c2 ^ -o ^ P (S) -o- (p) Formula 3 u Formula 35 FF NaO - <()> -> (C2H5Ol2P (S) -0 'Formula 36 Formula 37 Cl Cl NaO- ^ Oy-Cl> (CH30f2P (S) -0- / o) ~ cl Cl a Formula 38 Formula 39 ® / ^ S 0 ci-ch2-nQn ci \ ^ / Formula 40102 660 Na0 ~ (O) ~ N02 -> (C2H50-h2P (S) -0- <(OVNO; Formula U \ Formula Ul NaO - ^^ - Cl> (C2H50l2P (S) -0- (O) - Cl Cl Formula U2 Formula U Cl LZG Zd nr 3, order 461-79, cap. 95 + 20 copies. Price: PLN 45