SU959405A1 - Process for producing s-dialkylthiophosphoryl dithiocarbamates - Google Patents

Description

The invention relates to the field of chemistry of organophosphorus compounds, namely to a process for obtaining new _{S-dialkiltiofosforil-N-phenyl-N-5-boiling} dialkiltiofosforilditiokarbamatov ob- formula? I

-d - ^ - P (OR), (t), (OR) ,?

where R is lower alkyl.

Compounds of formula (I) can be used as starting of Great _{January ¹⁵} stances in organic synthesis for the introduction of a partner molecule tiofosfo-sterile. groups. The obtained compounds of formula (|) have complexing and extraction properties and can be used as organophosphorus complexing agents and extractants, which will make it possible to use them for the extraction and separation of metal ions in the analysis. Dithiocarbamates are among the most important insecticides that are currently widely used in practice; therefore, the compounds of formula (I) can be used in agriculture.

A known method of producing 5-alkyl-H-dialkylthiophosphoryldithiocarbamates, which consists in the interaction of dialkyldithiophosphoric acid with alkylaniline _1_.

However, 5-dialkylthiophosphoryl-N-phenyl-H-dialkylthiophosphoryldithiocarbamates of the formula (1) containing two phosphorus atoms, their properties and the method of their preparation are not described in the literature.

The preparation of compounds of formula (I) by a known method is not possible.

The aim of the invention is to develop an affordable method of obtaining

S-dialkylthiophosphoryl-N-phenyl-N-di '3,959,405 alkylthiophosphoryldithiocarbamates of the formula (I).

The goal is achieved _{with the} described way of obtaining ik- dialkiltiofosforil S-phenyl-P-M-dialkiltiot fosforilditiokarbamatov of formula (I), lies in the fact that the possibility to lay down dialkilditio rearrangement of compounds of formula (2) is difficult. Thus, the method for producing compounds of formula (|) is based on a new reaction.

No restrictions were found for this method. Under optimal conditions, sodium or potassium phosphate is reacted with N-phenylisocyanide dichloride in an inert polar 10th organic solvent at a temperature of 15 to 6 ° C.

The process is as follows.

To a solution of 1 Mb of sodium or potassium dialkyl dithiophosphate 15 in acetone or acetonitrile, 0.5 mol of N-phenylisocyanide dichloride is added. The mixture is heated for 30–15 minutes at 6 ° C, after 8-24 hours the precipitate and solvent are removed. The target compounds of formula I are purified by known techniques.

The reaction proceeds according to the scheme:

<ί ₅ Η ₅ Ν - (! ίι ₂ + Μί (^) ρ (σκ) _ζ -— “$

Initially, the substitution of two chlorine ato- ⁹⁵ mov a izotsianiddihloride on dithiophosphate group to form N-phenylbis (ditiofosforil) isocyanide of formula ₆ c _{h s h = c [sp (} s) (or) _{2] 2,} (2) which under the reaction conditions isomerized in S-dialkylthiophosphoryl-P-phenyl-P-dialkylthiophosphoryldithiocarbamate of formula (I). The ability soedi- ⁴⁵ neny formula (2) be isomerized to compounds of formula (I) not described in the literature and determines the specificity and the novelty of the invention. A similar rearrangement with 1,3 S — N 50 migration of the thiophosphoryl group in imidoyldithiophosphates was previously observed by ffj, however, the ability to isomerization of N-phenylbis (dithiophosphoryl isocyanide of formula (2) was discovered 55 for the first time. then in advance the pre-implementation of the method are: the use of the starting reagents isocyanide-dithiophosphate in a ratio of 1: 2, the process in a polar organic solvent capable of dissolving the original potassium dithiophosphate or sodium. It is convenient to use acetone, acetonitrile, ethyl'acetate as solvents; the process is carried out in the temperature range from 15 to 6 ° C. An increase in temperature promotes rearrangement, but decomposition of the target compounds is observed above 100 ° C.

The proof of the structure of the compounds of formula (I) was carried out using elemental analysis, IR, NMR (31 p) spectra.

The following absorption bands are indicated in the IR spectra (9, cm ~ *) 520-540 (PS), 640-660 (PS) 9901000, 1020-1060 (POC), 1160-1180 (POAlk), 1280, 1430-1460 (-NCS), 1495-1500, 1600, 3050-3080 (benzene core). NMR (31p) spectra indicate the presence of two phosphorus atoms with amidothiophosphate (δρ-60-bZ ppm) and dithiophosphate (δρ “, 78 - 81 ppm) surroundings. Identification of NMR, (31p) “'spectra is carried out using S- (Π, Ν-diethylthiocarbamoyl)' dithiophosphoric (δρ-75 - - 80 ppm) and P-phenyl- esters as standards i-dialkylthiophosphorylthiocarbs of the New (8 _p - 58--62 ppm) acids. ''

Example 1. Obtaining 5-diethylthiophosphoryl-M-phenyl-M-diethylthiophosphoryldithiocarbamate.

To a solution of 15.01 g (0.07 mol) of potassium diethyldithiophosphate in 50 ml of anhydrous ..acetone, 5.83 g (0.034 mol) of N-phenylisocyanide dichloride are added. The mixture is heated for 0.5 hours while boiling acetone, then 0.5 g of activated carbon is added and after 8-24 hours the precipitate of potassium chloride is filtered off. The filtrate was evaporated in vacuo of a water-jet pump, the residue crystallized. The product is purified twice by recrystallization from hot hexane. 15.2 g are obtained (yield 96% of U-diethylthiophosphoryl-Y-phenyl-M-diethylthiophosphoryldithiocarbamate with mp.

Found,%: C 38.20; H 3.03, P 12.98,

S> 4

Calculated,% ·. C 38.05; 2 ‘) 6; P 13.11.

op _f - 63, 0р ₂ - 81 ppm

Example 2. Obtaining 6-diisopropylthiophosphoryl-H-phenyl-Y-diisopropylthiophosphoryldithiocarbamate.

To a solution of 13 g (0.056 mol) of sodium diisopropyl dithiophosphate in 50 ml of anhydrous acetone, 4.87 g (0.02.8 mol) of N-phenylisocyanide dichloride are added. The mixture is heated for 15 minutes while boiling acetone, add 0.5 g of activated carbon and kept at room temperature for a day. Then the precipitate of sodium chloride is filtered off, the filtrate is evaporated in vacuo of a water-jet pump, the residue is crystallized. The product is recrystallized twice from hot hexane. Obtain 14.1 g (95% yield) of 6-diisopropylthiophosphoryl-N-phenyl-H-diisopropylthiophosphoryldithiocarbamate with mp 78.5-79.5 ° C.

Found,%: C 43.16; H 6.40; N 2.68; P 11.68.

C _lj? H ₃₃ N0 ₄ P ₂ 54

Calculated,%: C 43.10; H 6.24;

2.65; P 11.72.

δ _Ρί - 60, δ> ₂ - 78 ppm

When using the present invention provides the opportunity

72-73 ^a C. 5.25;

Η 5.29;

959405 6 synthesis of S-dialkylthiophosphoryl-I-phenyl-C-dialkylthiophos Foryldithiocarbamates with a yield of 95 ~ 9b%; reliable reproducibility of results; simplicity of the technology of the method, the method is carried out in one stage, the target compounds are easily isolated in analytically pure form; easy accessibility of starting compounds (dithiophosphates are produced by the chemical industry, isocyanide dichloride is obtained from phenyl isothiocyanate); expanding the range of dithiocarbamates and starting compounds in the synthesis of important insecticides, complexing agents and extractants.

to

Claims (2)

(54) The way to get new to S-DILCILIETHOSHOPHYLOBRAMATS oii) f, -P (OK) g i where R is lower alkyl. The compounds of the formula () can be used as starting materials in organic synthesis to introduce into the molecules of the partners of the thiophysporyl group. extraction and extraction properties and can be used as organophosphorus complexing agents and extractants, which will allow them to be used for the extraction and separation of metal ions in the analysis. Dithiocarbamates are among the most important insecticides widely used in modern practice, therefore compounds of the formula ( } can be used in agriculture. There is a known method of producing S-alkyl-M-dialkylthiophosphoryldithiocarbamates, which consists in the interaction of dialkyl dithiophosphoric acid with alkylroanide 1. However, Z-Dialkylthiophosphoryl-L-phenyl-H-dialkylthiophosphoryldithiocarbamates of formula (1), containing two phosphorus atoms, their properties and the method of their preparation are not described in the literature. The preparation of compounds of the formula (About a known method is not possible. The aim of the invention is to develop an affordable method for the preparation of 5-dialkylthiophosphoryl-M-phenyl-N-di395 alkyl thiophosphoryldithiocarbamates of formula 11). This aim is achieved by spin ,, syzaemym method for preparing S-dialkiltiofosforil-N-phenyl-N-dialkiltio7 fosforilditiokarbamatov of formula (I), zaklyuchakltsims that dialkyl sodium or potassium is reacted with N-fenilizotsianiddihloridom in inert floor rno- Yu th organic solvent at a temperature of from 15 to. The process is carried out as follows. To a solution of 1 M of dialkyl dithiophosphate of sodium or potassium in acetone or acetonitrile, 0.5 mol of N-phenylisocyanide dichloride is added. The mixture is heated for 30–15 min at 0 ° C, after 8–2 hours, a precipitate and solvent are removed. The target compounds of the formula I are purified by the known methods. The reaction proceeds according to the following scheme: (i5H5N.ciei2 + M () p (o: RJ -P {OB) 2 "First, the replacement of two atoms of chlorine in isocyanide dichloride by di-thiophosphate groups occurs with the formation of M- phenylbis (dithiophosphoryl) isacyanide of the formula (S) (OR) 21. (2) which, under the reaction conditions, is isomerized to 5-dialkylthiophosphoryl-K-phenyl-H-dialkylthiophosphoryldithiocarbamate of formula (|). The ability of compounds of the formula (2) to isomerize into a compound (About the literature is not described and determines the specificity and novelty of the invention A similar rearrangement with the 1.3 N migration of the thiophosphoryl group in imidoyl dyryphosphates was observed previously, ij, however, the ability to isolate the N-phenylbis (dithiophosphoryl) isocyanide of formula (2) was found for the first time, since it is not known at present what factors contribute isomerization, then it is difficult to rearrange the possibility of rearrangement of compounds of formula (2). Thus, the method of obtaining compounds of formula (i) is based on a new reaction. Restrictions for this method is not found. The optimal conditions for the implementation of the method are: the use of isocyanide-dithiophosphate reagents in the ratio of 1: 2, the implementation of the process in a polar organic solvent capable of dissolving the starting potassium or sodium dithiophosphate. It appears convenient to use as solvents acetone, acetonitrile, ethyl acetate; implementation of the method in the temperature range from 15 to. An increase in temperature contributes to the rearrangement, however, above 100 s, decomposition of the target compounds is observed. The structure of the compounds of the formula (() was tested using elemental analysis, IR, NMR (31p) spectra. In the IR spectra there are the following indicator absorption bands (, cm); 520-5 0 (PS), u-bbO (PS), 9901000, 1020-1060 (POC), 1160-P80 (POAlk), 1280, 1430-1460 (-N-CrS), 1495-1500, 1600, 3050-3080 (benzene core). NMR (31p) - the spectra indicate the presence of two phosphorus atoms with an amidothiophosphate (8l-60-63 ppm) and n (Sp - 81 ppm) environment. The NMRD31p identification of the spectra is carried out using the S-0 dialkyl esters as standards. (fl, N-diethylthiocacarbamoyl) dithiophosphonate (Sp-75 - - 80 ppm) and ether M-m-phenyl-dialkiltiofosforiltiokarbaminovoy (8r- 58 - - b2 ,, ppm) of acid EXAMPLE 1 "Preparation of 5-dietiltiofosforil-N-phenyl-N-dietiltiofosforilditiokarbamata. To a solution of 15.01 g (0.0–7 mol) of potassium diethyldithiophosphate in 50 ml of anhydrous .. acetone was added g (0.034 mol) of i-phenyl isocyanide dichloride. The mixture is heated for 0.5 hours at the boiling point of acetone, then 0.5 g of activated carbon is added and the precipitate of potassium chloride is filtered off after 8g24 hours. The filtrate is evaporated in a water jet vacuum; the residue crystallizes. The product is purified by recrystallization from hot hexane. 15.2 g are obtained (yield E (% 1-diethyl thiophosphoryl-M-phenyl-diethyl thiophosphoryl dithiocarbamate with m, pl, 72-73 C. Found:% C 38.20; H 5.25; 3.03, R 12.98, C, 5H25NO P254 Vichisleno,%: C 38.05; H 5.29; 2.46; P 13.11. 6pi- 63, 81 m, d., Example 2. Preparation of 5-diisopropylthiophosphoryl-H-phenyl-M-diisopropylthiophosphoryl dithiocarbamate. To a solution of 13 g (0.05 mol) of sodium diisopropyl dithiophosphate in 50 ml of anhydrous acetone, 4.87 g (0.028 mol) of N-phenyl isocyanide dichloride are added. The mixture is heated for 15 minutes at a boiling point of acetone, 0.5 g of activated carbon is added and the precipitate is filtered off at room temperature for sodium chloride, the filtrate is evaporated in a vacuum pump and the residue crystallizes. The product is recrystallized twice from hot hexane. Get T, g (yield 95) 5-di isopropylthiophosphoryl-N-phenyl-N-diisopropylthiophosphoryl dithiocarbamate with so pl. 78.5-79.5 ° C. Found,%: C 43.1b; H 6.40; N 2.68; Р 11.68, С, оНззМ04Р254 Calculated,%. C i3,10; H 6, 2.65; R 11.72, 8r - 60, 8r2 78 ppm When using the present invention, it is possible to synthesize 5-dialkylthiophosphoryl-M-phenyl-C-dialkylthiophosphoride dithiocarbamates with a yield reliable reproducibility of the results; the simplicity of the method, the method is carried out in one stage, the target compounds are easily separated in analytically pure form; easy availability of the starting compounds (dithiophosphates are manufactured by the chemical industry, isocyanide dichloride is obtained from phenyl isothiocyanate); expansion of the range of dithiocarbamates and starting compounds in the synthesis of important insecticides, complexing agents, and extragent. Claims of the invention The method of obtaining 5-dialkylthiophosphoryl-M-phenyl-M-dialkylthiophosphoryl dithiocarbamates of the general formula (1HH5K- &amp; R) (OK); P {OH) 2. where R is lower alkyl, which implies that sodium or potassium dialkyldithiophosphate is subjected to I interaction with N-α. nonyl isocyanide dichloride in an inert polar organic solvent at a temperature of from 15 to 60 ° C.