SU988821A1 - Process for preparing o,o-dialkyl-n-phenyl-n-(diphenyl-thiophosphenyl)-amidothionephosphates - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, and specifically to a method for producing 0,0-dialkyl-Y-phenyl-Y- (diphenylthiophosphinyl) amidothionophosphates of the general formula (RO) ₂ PNP (S) (C _fe H ₅ ) ₂ (1) s with ₆ H ₅ where R is lower alkyl.

Compounds of formula (1) can be used as starting materials in organic synthesis for the introduction of thiophosphoryl group substrates into molecules. The amidothionophosphates of formula (I) form complex compounds with thiophilic metal ions, which are extracted with chloroform or carbon tetrachloride from acidic media, so they can be used as organophosphorus complexing agents and extractants for concentration and separation of metals in the analysis. Amidothionophosphates (I) and the method for their preparation are not described in the literature.

A known method of producing dithionphosphorylalkylamides by the interaction of diesters of halogenothiophosphoric acids with sodium substituted amides of dialkylthiophosphoric acids G 1].

c However, using this method it is not possible to obtain o, O-dialkyl-L ~ phenyl-L1- (diphenylthiophosphinyl) amidothionophosphates. There is also known a method for producing O, O-diethyl- (N-phenyl-I-diethoxyphosphorylamido) thionphosphate, which consists in the interaction of diethylanilidophosphate- ¹ with diethoxyphosphoryl sulfene chloride in the presence of base {2]. The disadvantages of this method are the use of low temperatures,.

difficult accessibility of phosphoryl sulfene chlorides; low yield (-> 40%) of target compounds. The method is not universal, predict NOSTA synthesis vozmozh_ _n O, O-dialkyl-N-fenil20 (difeniltiofosfinil) amidotionfosfatov of formula (I) according to this method is not possible. The purpose of the invention is the development of an affordable way to obtain new about, O-dialkyl-M-phenyl-Y- (diphenylthiophosphinyl) amidothionophosphates of the formula (I).

The goal is achieved according to the method for producing 0,0 -di30 απκΗΠ-Ν-φβΗϋπ-Ν- (diphenylthiophosphi988821 nyl) amidothionphosphates, namely, that ammonium dialkyl dithiophosphate is reacted with N-phenyliminodiphenyl chlorophosphinate in an inert organic solvent of 20 ° C.

The process is described by the following scheme (II)

Cl (lit)

-Nfyc?

(Iv) to (1)

The first stage of the process is a nucleophilic substitution at the tetrahedral phosphorus atom and leads to the formation of phosphazo compounds (IV), which under the reaction conditions easily undergo phosphase-phosphoryl rearrangement with 1,3 S- »N migration of the thiophosphoryl group with the formation of the target products of formula (I). The formation of phosphazo compounds (IV) was recorded by observation of the process by NMR ( ³⁴ P) spectroscopy. The ability of compounds (IV) to be isomerized to compounds (I) is not described in the literature and determines the novelty and specificity of the present invention. In £ 2), a similar rearrangement was made with the migration of the phosphoryl group, however, the complex course of the reaction allows us to interpret the formation of final products, excluding the possibility of such isomerization.

Phosphase-phosphoryl rearrangement with migration of the thiophosphoryl group is shown for the first time. Since it is not currently known which factors contribute to isomerization, it is difficult to predict in advance the possibility of rearrangement of type (IV) compounds. Thus, the method for producing compounds of formula (I) is based on a new reaction.

No restrictions were found for this method. The optimal conditions for implementing the method are. The use of starting reagents in a ratio of 1: 1. Implementation of the process in an inert organic solvent, capable of dissolving the initial crystalline substances. It is convenient to use dioxane, acetone, ethyl acetate as solvents. The implementation of the method in temperature <

the range of 20-100 ° C. An increase in temperature accelerates the rearrangement process, however, above 150 °, compounds (1) are disproportionate. ' The structure of the compounds of formula (I) was proved using IR and NMR ( ³⁴ P) spectra, the composition was confirmed by elemental analysis, and the purity was controlled by elemental analysis and spectral methods.

The following absorption bands are indicated in the IR spectra, cm · ¹ ): 615-620 (P = S in phosphinates), 645-650 (P = S in amidophosphates) 900-905, 915-925 (PN), 980-1000 , 1020-1050, (POC), 1150 (POAIk), 1450 (P-C6H5) S 1495-1500, 1600, 3065-3070 (benzene core), there is no absorption l) (P = N) at 1330-1370 cm * ⁴ . In the NMR ( ³⁴ P) spectra, two signals of the same intensity of ³⁴ P nuclei with ά4 · ϊρ ^ 65, s7 ^g 31 _p 66 ppm are observed, which is characteristic of the diphenylthionphosphinate and dialkoxythionamidophosphate environments of the phobfor atoms. During the hydrolysis of compounds (1), along with other products, an image is observed. O, O-dialkyl-b-phenylamidothionophosphates.

Example 1. Obtaining O, O-diisopropyl-M-phenyl-L ^ -Diphenylthiophosphinyl) amidothionophosphate.

A mixture of 7.0094 g (0.0303 g mol) of ammonium diisopropyl dithiophosphate and 9.4521 g (0.0303 g mol) of N-phenylaminodiphenyl chlorophosphinate in 250 ml of anhydrous dioxane is heated at boiling of the solvent for 5 minutes, 1 g of activated carbon is added and kept at room temperature for 8 hours. The reaction mass was filtered, the filtrate was evaporated in vacuo. The residue was dissolved in anhydrous ether, the insoluble precipitate was separated. A large amount of pentane was precipitated from the ethereal solution. For additional purification, the substance was dissolved in 25 ml of anhydrous ether and 150-200 ml of pentane were reprecipitated, and the crystals were dried in vacuo. 13.5 g (yield 91%) of 0,0-diisopropyl-A'-phenyl-L1- (diphenylthiophosphinyl) amidothionphosphate are obtained with a melting point of 104-105 ° С, ο ⁴ 3ΐρ · 65, t / ii р 66 ppm Found,%: C 58.71; Η 5 $ 99; P 12.65; Calculated, ®: C, 58.90; H 5.93;

IR (-ί, cm * ⁴ ): 620 (P = S in phosphinates, 645) P = S in amidophosphates), 985, 1000 (РОС), 905, 925, (PN), 1150 (РОС ₃ Н ₇ ), 1450 (PС ₆ Н ₅ ), 1495, 1600, 3070 (benzene ring); V absorption is absent (P = N).

Into a mixture of 0.01 g mol of ammonium diisopropyl dithiophosphate, 0.01 g mol of N-phenylaminodiphenyl chlorophosphinate in 100 ml of absolute ethyl acetate

2 'add 1 g of activated carbon and the reaction mass is kept at 20 ° C for 5-7 days. The target product is isolated and purified by a similar method. The yield of 0,0-diisopropyl-Ν-φθΗππ-Ν- (diphenylthiophosphinyl) amide-5 dthionophosphate 85%.

Example 2. Obtaining 0,0-diπροπΗΠ-Ν-φβΗππ-Ν- (diphenylthiophosphinyl) -amidothionophosphate.

A mixture of 15.0249 g (0.065 g mol) of 10 aglmonium dipropyl dithiophosphate and 20.9609 g (0.065 g mol) of N-phenyliminodiphenyl chlorophosphinate in 250 ml of anhydrous dioxane is heated at boiling for 5 minutes, 1 g of activated charcoal is added and kept at room temperature for 12 hours. The reaction mass was filtered, the filtrate was evaporated in vacuo. The residue was dissolved in ether, the insoluble precipitate was separated. From a 20 ether solution, the target product is precipitated with pentane. Released thick oil is twice subjected to molecular-film distillation at 150 ° C and a pressure of 0.02 mm Hg 25 28 g (88% yield) of 0.0-dipropyl-Y-phenyl-N- (diphenylthiophosphinyl) amidothionphosphate with Fri; ⁰ 1.6095, <Lz _r 65,

ppm Found,%: C 58.67; H5.93; P 13.09; C ₂₄ HggNC ^ PgSg. Calculated,%: 30

C, 58.90; H 5.93; P 12.68: IR (V, cm ^{- 1} ): 615 (P = S in phosphinates), 650 (P = S in amidophosphates), 900, 915 (PN), 980, 1020, 1050 (POC), 1150 '(ROS _E N ₇ ), 1450 (RS ₆ N ₅ ), 1500, 1600, ₃₅

3065 (benzene core), no absorption ^ (P = N).

0.05 g-mol of ammonium dipropyl dithiophosphate is dissolved in 100 ml of anhydrous dioxane when heated, after which 0.05 g-mol of N-phenyliminodiphenyl chlorophosphinate is added. The reaction mass is heated under reflux at 50-65 ° C for 8-10 hours, then 0.5 g of activated carbon is added to coagulate the precipitate. The next day, 0,0-dipropyl-P-phenyl-M (diphenylthiophosphinyl) amidothionphosphate 'is isolated by a similar method.

Yield 65%, when standing for a month. the product crystallizes.

Using the present invention, it is possible to synthesize new O, O-dialkyl-Y-phenyl-N- (diphenylthionphosphinyl J amidothionphosphates with a yield of 88-91%, which is 48-30% higher than the known methods for producing amidophosphates with two phosphorus atoms. Moreover, the method is characterized by reliable reproducibility of results, versatility and simplicity of the technology.The method is carried out in one stage, the target compounds are easily isolated in analytically pure form, the starting compounds are easily accessible. substances in the synthesis of organophosphorus complexing agents and extractants.

Claims (2)

nyl) amidothionic phosphates, which implies that ammonium dialkyldithiophosphate is reacted with N-phenyl aminodiphenyl chlorophosphinate in an inert organic solvent at 20-100 ° С. The process is described by the following scheme (oijP5S tlc 5) III) ci (III 1Ч5Ч |, А. C6-H5-N - l &amp;) HW -. (C5Н5), Р-1г-Р ((ok) g, ( tl The first stage of the process is the nucleophilic substitution of the tetrahedral phosphorus atom and leads to the formation of phosphazium compounds (IV), which under the reaction conditions easily undergo a phosphazophosphoryl rearrangement with a 1.3 S migration of the thiophosphoryl group to form the desired products of the formula Ly ( I). The formation of phosphazo compounds (IV) was observed by observing the progress of the process by the method of NMR P) spectroscopy. The stem is connected (IV) isomerized into the compound (not described in the literature and determines the novelty and specificity of the present invention. 21 suggested a similar rearrangement with the migration of the phosphoryl group, but the complex course of the reaction allows to treat the formation of end products, excluding possibility of such isomerization. The phosphase-phosphoryl rearrangement with the migration of the thiophosphoryl group is shown for the first time. Since it is not currently known which factors contribute to isomerization, it is difficult to suggest in advance the possibility of rearrangement of compounds of type (IV). Thus, the method of obtaining compounds of formula (IJ is based on a new reaction. No limitations were found for this method. Optimal conditions for the implementation of the method are. Use of initial reagents in a 1: 1 ratio. The process is carried out in an inert organic solvent capable solution Source crystalline substances. Convenient. It is proved to use dioxane, acetone, ethyl acetate as solvents. The process can be realized in the temperature range of 20-100 ° C. The temperature rise accelerates the rearrangement process, however, the disproportionation of compounds (1) occurs above 150. Proof of the structure of compounds of the formula G1) is carried out using IR and NMR (P) spectra, the composition is confirmed by elemental analysis data, purity is monitored by elemental analysis and spectral methods. In the IR spectra there are the following indicator absorption bands (-0, cm-): 615-620 (in phosphine-. So), 645-650 (in amidophosphates) 900-905, 915-925 (PN), 980-1000, 1020-1050, (POC), 1150 (POAIk), l450 (P-SbH5-), 1495-1500, 1600, 3065-3070 (benzene core), there is no absorption l) () at 1330-1370 cm-. In the NMR (P) spectra, two signals of the same intensity of nucleus P with cfSfp 65, MD are observed, which is characteristic of diphenylthionphosphinate and dialkoxycitonamidephosphate environment of the foiffor atoms. During the hydrolysis of compounds (tj, O, O-dialkyl-H-phenylamidotoionic phosphates are formed along with other products. Example 1, Preparation of O, O-diisopropyl-M-phenyl-M- (diphenylthiophosphinyl) amidothionophosphate. Mixture 7.0094 g (0.0303 g-mol) of ammonium diisopropyl dithiophosphate and 9.4521 g (0.0303 g-mol) of N-phenylaminodiphenyl chlorophosphinate in 250 ml of anhydrous dioxane are heated under reflux for 5 minutes, 1 g of activated carbon is added and kept at room temperature 8 the reaction mass is filtered, the filtrate is evaporated in vacuo. The residue is dissolved in an anhydrous ether, an insoluble precipitate is separated. 6% of the amount of pentane is precipitated from the ether solution of the target product. To purify the substance, it is dissolved in 25 ml of anhydrous ether and re-precipitated 150-200 ml of pentane, the crystals are dried in vacuo, 13.5 g are obtained (91). %) 0,0-diisopropyl-K -phenyl1 M- (diphenylthiophosphynyl) -amido-ionophosphate with m.p., 65, p „66 m. Found: C 58.71 H 5.99; R 12 , 65; C2.H2gNOr, P2S2. Calculated; C 58.90; H 5.93; Fl2.68. IR (-J, cm-): 620 (in phosphinates, 645) in amidophosphates), 985, 1000 (POC), 905, 925, (PN), 1150 (POC 3 H), 1450 (), 1495, 1600, 3070 ( benzene ring), there is no absorption of l) (). Into a mixture of 0.01 gmol ammonium diisopropyl dithiophosphate, 0.01 I mol N-phenylaminodiphenyl chlorophosphinate in 100 ml of absolute ethyl acetate, 1 g of activated carbon is added and the reaction mass is kept at 20 ° C for 5-7 days. The desired product is isolated and purified by a similar procedure. Yield O, O-diisopropyl-N-phenyl-N- (diphenylthiophosphinyl) amidothionophosphate 85%. Example 2. Obtaining O, O-dipropyl-N-phenyl-N- (diphenylthiophosphinyl) -amidothionophosphate. A mixture of 15.0249 g (0.065 g-mol) of dipropyl dithiophosphate and 20.9609 g (0.065 g-molJ of N-phenyliminodiphenylchlorophosphinate in 250 ml of anhydrous dioxane is heated at the boiling point for 5 minutes, 1 g of activated carbon is added and held at room temperature 12 h. The reaction mass is filtered, the filtrate is evaporated in vacuo. The residue is dissolved in ether. The insoluble precipitate is separated. Lt. From the ethereal solution, the target product is precipitated with pentane. The separated thick oil is subjected to molecular-film distillation twice at a pressure of 0.02 mg / i Hg 28 g (88% yield) 0.0-di popil-N-phenyl-N- (diphenylthiophosphinyl) amidothionic phosphate with tij 1.6095, 65, о31р 66 ppm Found,% C 58.67; H5.93; R 13.09; C H29N02 252 Calculated,% C 58.90; -H 5.93; R 12.68: IR (V,): 615 (in phosphinates), 650 (in amidophosphates), 900, 915 (PN), 980, 1020, 1050 (POC), 1150 (POCeH7), 1450 (PC (, H5), 1500, 1600, 3065 (benzene core), no absorption (). 0.05 g-mol of ammonium dipropyl dithiophosphate is dissolved by heating in 100 ml of anhydrous dioxane, after which it is added 0.05 gmol of N-phenyliminodiphenylchlorophosphate. The reaction mass is heated under reflux at 50–65 ° C for 8–10 h, then 0.5 g of activated carbon is added to coagulate the precipitate. The next day, O, O-dipropyl-N-phenyl-N- (diphenylthiophosphinyl) amidothionophosphate was isolated in a similar manner. Yield 65%, when standing for 2 months. the product crystallizes. Using the present invention, it is possible to synthesize new O, O-dialkyl-M-phenyl-N- (diphenylthionphosphinne) amidothionic phosphates with a yield of 88-91%, which is 48-30% higher than the known methods for the preparation of amidophosphates with two phosphorus atoms. In addition, the method is characterized by reliable reproducibility of results, versatility and simplicity of the technology. The method is carried out in one step, the target compounds are easily isolated in an analytically pure form, the starting compounds are easily accessible. The method expands the range of starting materials in the synthesis of organophosphate complexing agents and extractants. The invention of the method of producing 0, 0-dialkyl-K-phenyl-N- (diphenylthiophosphinyl) hydrochloride ion phosphates of the general formula (KO P - N - ($) (Cll5, bHs where R is lower alkyl, implying that ammonium dialkyldithiophosphate is subjected to interaction with N-phenyliminodiphenylchlorophosphinate in an inert organic solvent at 20-100 s.Sources of information taken into account in the examination 1.Purdela D., R. Valchanu Chemistry of organic phosphone compounds, M ,, Chemistry, 1972, pp. 460. 2.Gololobov Yu.G. et al. Phosphazo-amidine rearrangement of imidtiopyrophosphates, JO, 1979, 49, 11, p. 2624.