SU509597A1 - Method for producing acid phosphorus amides - Google Patents

Description

The invention relates to an improved process for producing phosphorus acid amides of the general formula

| Кл1ВВ} Г)

: Where R is an alkyl or alkoxy; t1 R and R are hydrogen or alkyl;

 0.1, 2.10

These compounds. are applied in

different areas of national economy,

For example, as extractants for 1 vstelenie

 valuable metal ov ...

; A known method for producing amides of acidic phosphorus lozenges is the interaction of amines with acid chlorides, phosphorus. An excess of the starting amine can be used as an acceptor of liberating hydrochloride chloride. In this case, however, side reactions are possible and product yield does not

: high 1 Therefore, usually the interaction of amines with chlorant-additives of phospho acids; ra in the presence of tertiary avimoE

as acceptors of hydrogen chloride, bowl 25

total pyridine. Target products when i do this with high yield.

The disadvantages of this method are the difficulty of removing from the reaction medium bulk, difficult-to-filter precipitates pyridine hydrochloride and the formation of significant amounts of toxic waste water.

In order to simplify the process according to the proposed method, ion exchange resins of the basic type are used as hydrogen chloride acceptors.

At the end of the reaction, the phosphorus acid amide formed is separated from the ion exchange resins by decantation. The resin is regenerated with a solution of soda and reused 6 synthesis.

The reaction goes well under mild conditions, which is especially important in the preparation of the thermally unstable amides of phosphorus acids containing a secondary atom of the nitrogen amide group.

Claims (4)

: The process can be carried out in an inert organic solvent, such as chloroform. Target products, using known techniques, are used for all experiments in the following examples: ion-resin: on VP-1 or VP-3 resin in the main fbi, dried directly before use in vacuum (1 mm Hg) at 50 C for 4 hours. The capacity for hydrogen chloride is determined by the method of non-aqueous potentiometric titration in dimethylformamide. For the resin VP-1, the capacity for chlorine-hydrogen 3 is 10 mol / g resin, -3 for the resin VP-3 2.7 1O g. eq / g CMO ly. Example. Methylamide dehexyl-acetic acid, 28.5 g (OD mol) of dihexyl chlorophosphate — in 1OO ml of dry chloroform at a temperature of from 0 to 5 ° C .. are added dropwise to a mixture of 6.2 g (0.2 mol) of methylamine in 10 O of ml of chloroform and 19.4 g dry resin VP-1 (2p9-th and excess). The mixture is left for four days at room temperature, then the resin is filtered off, the solvent is distilled off and the residue is distilled in a vacuum. 16.3 g of the expected product are obtained. Yield 58.5%; t. Kip, 173-175S / 1 mm p Art., P.20 1.4361; 0.9671. Found,%: C 55.64, H 1O, 92, N 5.21 P 11.21. h ° ° s Calculated,%; C 55.88; H 1O, 82; N 5, O1; R 11.09, IR spectrum of the product, cm-. -. (P-O 3240 (NH) .3f-41 In the spectrum: NMR P: signal P 12 m P P and m in P 2. Trisbutylamide tpoc, l fororic acid .. 15.35 g (OD mol) of phosphorus oxychloride in 1OO ml of dry chloroform at a temperature from 0 to dropping 43.8 g (0.6 mol) of butylamine, 60 g of dry resin VP -1 and 15 ml of dry chlorofom. The mixture is left at room temperature for four, then the resin is filtered off, and the filtrate is successively washed with brine, water, 5% soda solution and until neutral. Then the solvent is distilled off and the product is dried in vacuum (1 mm Hg) at 7 p-80 ° C. 20.5 g of the desired product are obtained in the form of a viscous, dark, oily liquid, OST The yield is 76.7%; n | O, 1.4645; d2O Oh, 9687. Naive,%: C 54.65; And 11.85; i.N 15.85; R 11.64. 3 Calculated,%: C 54.71; H 11.48; N 15.95; R 11.75. IR; spectrum of schudukta, cm: 1173 (P 0 0) 200 (N H). NMR on drugs J-P 1O m. N. P P m e e R 3. Bisbutylamnd butiponic acid. 17.5 g (0.1 mol) butnll 11x.1 orphosphonate 100 ml of dry chlorof;)) marie temperature from 0 to added dropwise to a mixture of 51.6 g (0.4 mol) of dibutylamine, 90 g of dried VP-3 and 15O ml of dry chlorophoma. the mixture was suspended at room temperature for 5 days, then heated for 4 hours during spraying, the resin was filtered, and the fi rm was removed as in Example 2, Then the solvent was distilled, and the product was dried in vacuum (1 mm Hg, Art. ) at 70-8 ° C, there are 28.9 g of the desired product in a perfectly viscous, dark, oily liquid. Yield 77.9%; 1.4562, 9P d 4 0.9497; Found: C .66.32; H 12.14; M 8.14; R 8.21, So 45 ° “2 Calculated. %: C, 66.72; H 12.60; N 7.81, P 8.71. IR spectrum of the product, 1195 (). NMR on the tracks G 34 m, d. P P and e e R 4. Butylphosphinic acid dibutylamide. 19.6 g (O, 1 mo7sh) of dibutylphosphinic acid chlorohydride in 1OO ml of dry chloroform were added dropwise to a mixture of 25.8 g (0.2 mol) of dibutylamine, 9O g of VP-Z dry gum in basic form and 15C) of dry chloroform . The mixture was left at room temperature for two days, and then heated for 2 hours at the boiling point of chloroform. After cooling the reaction mass, the solution is decanted from the resin. With gognav chloroform in vacuum at a residual pressure of 10 mm Hg, st., 9.1 g of n-reacted dpbutylamine are distilled off. The bottoms are cooled and dissolved in 1OO ml of heptane. The solution is washed after a successively 1O% molar hydrochloric acid solution, with water, with a 3% soda solution and with water until neutral. The solvent is then distilled off, and the product is dried in vacuo (1 mmHg, art.) At 80-90 4; I get; 26.1 g of the intended product as a viscous oily liquid. Yield 9О, 8%; п2О 1,4661, Found,;,: (.; 66.28; H 12.71; N 5, О Р 10.52 С-, .Н ",. ГОР. 1Ь 3 Ь Calculated ,%: C 66.43; H 12.45; N 4.84; P 10.72. Rjl31 B C1 x.) E P signal R. 18 m Example 5. Bisbutylamide, Oct. phosphoric acid. 24.7 g (0.1 mol) of octylphosphoric acid dichlorohydrin in 10O ml dry chloroform at -5-0 dropwise a mixture of 29.2 g (0.4 mol) butnlamine, 85 g of dry VG1-1 resin in the main form and 150 ml of dry chloroform. The mixture is left to stand at room temperature for two days. The solution is decanted from cm fibJ. After distillation of chloroform and an excess of butylamine, the residue is dissolved in 1OO ml of heptane. The solution is washed as in 4. Then the solvent is distilled off the product and the sudat in vacuum (1 mm Hg, Art. At 4 ° -50 ° C. 25.02 g of the desired product is obtained as a viscous oily liquid. You run 78.2%; DL 1.454 O. Found; %; C 60.14; H 11.69; N 8.87; R 9.7. C1b 37 2 2P Calculated,%: C 6 O, O5; H 11.58; N 8.75; .Р, 6.68 Г1 Р and ме Р 6. Hexabutyltrioamide of phosphoric acid, 15.35 g (О, 1 mol) of phosphorus oxychloride in J.OO ml of chloroform are added dropwise to a mixture of 77.4 g (0.6 mol) of dibutylamine, 70 g of dry Sm-1 VP-1 in basic form and 15 O ml of chloroform. The mixture is left at room temperature for two days and then heated for 2 hours at the boiling point After cooling, the solution is drained from the resin and the solvent is distilled off. Then under vacuum at a residual pressure of 10 mm Hg, St, 29.7 g of unreacted dibutyl amine are distilled off and at 1 mm Hg, St. 32.8 g of hexahexabutyptrisamide of phosphoric acid Yield 75, 6%; t, bale 190-198 ° C / 1 mmHg St. P. 1.4638. Claim of the invention The method of obtaining phodoxy acid amides of general formula Rn () 3-rxP 0 where R is alkyl or alkoxy; R and R are hydrogen or alkyl; . g 0,1,2, interaction of amines with phosphorus acid chlorides in the presence of hydrogen chloride acceptors, characterized in that, in order to streamline the process, ion-exchange is used as hydrogen chloride acceptors; basic type resins.