RU2296768C1 - Method for preparing n-diphenylphosphoryl-n′-alkyl-(c6-c10)-ureas - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to derivatives of urea. Method is carried out by oxidation of diphenylchlorophosphine with sulfuryl chloride at temperature 20-25°C in carbon tetrachloride medium. Formed diphenylphosphinic acid chloroanhydride is subjected for interaction with sodium cyanate in acetonitrile medium in the presence of anhydrous magnesium chloride as a catalyst at temperature 20-25°C followed by the addition reaction of formed diphenylphosphoryl isocyanate to n-alkylamines at temperature 20-25°C in acetonitrile medium used as a solvent. Invention provides simplifying method and synthesis of highly pure substance and decreasing energetic and economy consumptions. Synthesized compounds can be used in technology for treatment of radioactive waste in radiochemical manufacture.

EFFECT: improved method of synthesis.

5 ex

Description

The invention relates to the field of organic chemistry, and more specifically to methods for producing organic compounds containing phosphorus in the form of phosphorus in the form of heteroatoms - N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) ureas.

The invention can be most effectively used in the preparation of extractants for radiochemical industries, including for the isolation of highly radioactive elements americium and europium. The compounds mentioned make it possible to concentrate and remove the most radioactive waste from technological solutions and thereby relieve environmental stresses that have developed in radiochemical plants.

A known method of producing N-diphenylphosphoryl-N'-alkyl (C ₃ -C ₅ ) urea by the interaction of diphenylphosphoryl isocyanate (synthesized from silver cyanate and diphenylphosphinic acid chloride) with the corresponding primary amines in a solution of benzene [K. Utvary, E. Freundlinger, V. Gutmann "N-Diphenylphosphinyl-harnstoffe", Monatshefte fur Chemie, 97, No. 2, 348-360 (1966)]. The disadvantage of this method is the use for the production of diphenylphosphoryl isocyanate of expensive silver cyanate.

A known method of producing N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea, which we have selected as a prototype [V.P. Morgalyuk, A.M. Safiulina, I.G. Tananaev, E.I. Goryunov , I.B. Goryunova, G.N. Molchanova, T.V. Baulina, E.E. Nifantiev, B.F. , 403, No. 2, 201-204 (2005)]. It includes two individual stages. The first stage is the interaction of diphenylphosphinic acid chloride with sodium cyanate in the presence of catalytic amounts of anhydrous magnesium chloride in acetonitrile when the reaction mixture is boiled (80-85 ° С), followed by isolation of the resulting diphenylphosphoryl isocyanate by distillation in vacuo, the second stage is the interaction of the obtained isocyanine (C ₆ -C ₁₀₎ amine benzene solution at a temperature of 20-25 ° C with subsequent isolation of the N-diphenylphosphoryl-N'-alkilmochevin with conventional special.

The disadvantage of this method is that its first stage requires the purification of the resulting product by high vacuum distillation, which complicates the synthesis on an enlarged scale. In addition, the starting material of the first stage (diphenylphosphinic acid chloride) is an expensive product and is not produced on an industrial scale.

The objective of the invention is to develop a new method for producing N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea, which is based on available raw materials and is efficient and technological.

The problem is solved by oxidation of diphenylchlorophosphine with sulfuryl chloride at a temperature of 20-25 ° C in a medium of carbon tetrachloride, resulting in the formation of diphenylphosphinic acid chloride, which is subjected to interaction with sodium cyanate in an acetonitrile solution in the presence of anhydrous magnesium chloride as a catalyst at a temperature of 20-25-25 ° C followed by the reaction of addition of the resulting diphenylphosphoryl isocyanate to n-alkyl amines at a temperature of 20-25 ° C in a solvent medium, as otorrhea using acetonitrile.

The essence of the invention lies in the fact that N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea is obtained according to the scheme using diphenylchlorophosphine as the starting compound and with a change in the set of actions in the synthesis process.

Obtaining N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea proceeds according to the following scheme:

First, a commercially available product, diphenylchlorophosphine, is oxidized with sulfuryl chloride in carbon tetrachloride at 20-25 ° C, which leads to the production of diphenylphosphinic acid chloride; subsequently, the solvent and other volatile components of the reaction mixture are removed in vacuo. Then, a solvent, acetonitrile, 2.5 mol% of anhydrous magnesium chloride, which is a catalyst, and sodium cyanate, are successively added to the same reactor; after stirring at room temperature for one hour, the corresponding primary amine is added to the reaction mixture containing the diphenylphosphoryl isocyanate formed in the acetonitrile solution. After stirring for one hour at room temperature, the reaction mixture is decomposed with water, the precipitate of the desired N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea is filtered off, washed and dried in air.

A significant difference of the proposed method from the known solution is that previously diphenylchlorophosphine is oxidized with sulfuryl chloride at a temperature of 20-25 ° C in a medium of carbon tetrachloride to obtain the starting diphenylphosphinic acid chloride, and the interaction of this acid chloride with sodium cyanate is carried out at room temperature (20-25 ° C), and acetonitrile is used as a solvent in the interaction of diphenylphosphoryl isocyanate with n-alkylamines, and therefore the claimed solution is consistent is the criterion of novelty.

A specific method for the preparation of N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) ureas is given in the following examples.

Example 1. N-diphenylphosphoryl-N'-n-octylurea

Into a one-necked pear-shaped flask equipped with forshtos with a dropping funnel, an argon supply and a liquid shutter filled with conc. sulfuric acid, put a solution of 7.28 g (0.033 mol) of diphenylchlorophosphine in 15 ml of abs. carbon tetrachloride, while stirring on a magnetic stirrer in an argon atmosphere at room temperature for 1 hour 20 minutes, a solution of 5.4 g (0.040 mol) of freshly distilled sulfuryl chloride in 10 ml of abs. carbon tetrachloride, after adding a solution of sulfuryl chloride, the mixture is stirred for another 20 minutes at this temperature, the solvent and other volatile components of the reaction mixture are removed in a vacuum of a water-jet pump (10-12 mm Hg) (20 min), and then kept in a mechanical vacuum pump (~ 1 mmHg) (1 hour). According to the ³¹ P NMR spectrum, the residue contains 99.8% diphenylphosphinic acid chloride. The residue is dissolved in 50 ml of abs. acetonitrile; 0.080 g (0.840 mmol) of finely ground anhydrous magnesium chloride was added to the resulting solution, stirred on a magnetic stirrer until the latter was completely dissolved (~ 5 min), 4.29 g (0.066 mol) of sodium cyanate added, the mixture was stirred on a magnetic stirrer for 1 h at room temperature. According to the ³¹ P NMR spectrum, the reaction mixture contains 97.8% diphenylphosphoryl isocyanate. 4.27 g (0.033 mol) of n-octylamine are added to the resulting suspension, stirred on a magnetic stirrer for 1 h at room temperature, 50 ml of distilled water are added, stirred on a magnetic stirrer for 1 h at room temperature and left overnight. The precipitate is filtered off, washed with a mixture of 34 ml of distilled water and 6 ml of acetonitrile, then with a mixture of 56 ml of 1% hydrochloric acid and 4 ml of acetonitrile, and then with distilled water (4 x 30 ml). Dried in the air. The yield of N-diphenylphosphoryl-N'-n-octylurea was 12.0 g (97.7%), mp. 155-156 ° C. ¹ H NMR spectrum (CDCl ₃ , δ, ppm): 0.85 t (3H, CH ₃ , ³ J _H-H = 6.7 Hz), 1.05-1.42 m [12 N, (CH ₂ ) ₆ ], 3.06 dt (2H, C H ₂ NH, ³ J _CH-H = 6.7 Hz, ³ J _CH-H = 6.0 Hz), 6.79 t (1H, N H CH ₂ , ³ J _H-H = 6.0 Hz), 7.33-7.46 m (4H, mC ₆ H ₅ ), 7.47-7.57 m (2H, pC ₆ H ₅ ), 7.67-7.83 m (4H, oC ₆ H ₅ ), 7.96 d [1H, NHP (O), ² J _H-P = 11.0 Hz]. Nuclear Magnetic Resonance Spectrum ³¹ P { ¹ H}, (CDCl ₃ , δ, ppm): 24.31 s. ¹³ C NMR spectrum { ¹ H}, (CDCl ₃ , δ, ppm): 13.97 s (CH ₃ ), 22.52 s (CH ₃ C H ₂ ), 26.63 s (CH ₃ CH ₂ C H ₂ ), 29.08 s [CH ₃ (CH ₂ ) ₂ C H ₂ ], 29.13 s [CH ₃ (CH ₂ ) ₃ C H ₂ ], 29.60 s [CH ₃ (CH ₂ ) ₄ C H ₂ ], 31.68 s [CH ₃ (CH ₂ ) ₅ С Н ₂ ], 40.03 s (CH ₂ NH), 128.45 d [С ^{2 (6)} НР, ² J _C-Р = 13.2 Hz], 131.31 d [С ^{3 (5)} НР, ³ J _CP = 10.3 Hz], 131.31 d (C ¹ P, ¹ J _C-P = 128.4 Hz), 132.27 d (C ⁴ HP, ⁴ J _CP = 2.2 Hz), 155.98 s (C = O). Found,%: C 67.84, H 7.87, N 7.41, P 8.32. C ₂₁ H ₂₉ N ₂ O ₂ P. Calculated,%: C 67.72, H 7.85, N 7.52, P 8.32.

Homologous substances obtained in a similar manner are shown in the table (examples 2-5).

As starting compounds, technical diphenylchlorophosphine (CAS Index [1079-66-9], Acros, 95%), sulfuryl chloride (CAS Index [7791-25-5], Acros, 98.5%), anhydrous magnesium chloride were used (CAS Index [7786-30-3], Aldrich, ≥98%), sodium cyanate (CAS Index [917-61-3], Aldrich, 96%), n-hexylamine (CAS Index [111-26- 2], Acros, 99%), n-heptylamine (CAS Index [111-68-2], Acros, 99 +%), n-octylamine (CAS Index [111-86-4], Acros, 99 +%), n-nonylamine (CAS Index [112-20-9], Acros, 98%), n-decylamine (CAS Index [2016-57-1], Aldrich, ≥98%). As solvents used domestic carbon tetrachloride (GOST 20288-74) and acetonitrile [TU 6-09-3534-87 (1-4 rev.)].

This invention allows to obtain N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea with a yield (counting on diphenylchlorophosphine) of at least 91% (see table) and with a high (at least 98%) degree of purity. The whole process, including the synthesis of the starting diphenylphosphinic acid chloride, takes place in a single reactor ("one-pot" reaction). All stages are carried out at room temperature, do not require high vacuum distillation of intermediate products or other complex procedures. The duration of the process is ~ 6 hours, i.e. 2-3 times shorter than the prototype method. All this, in aggregate, leads to a decrease in energy and labor costs and, as a result, to a significant reduction in the cost of N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) ureas, which, in turn, will make their practical use a reality as extractants.

Table.
Yields, constants, and elemental analysis of N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) ureas Ph ₂ P (O) NHC (O) NHAlk Example No. Alk Exit, % T. pl., ° C

Gross formula FROM N N P 2 nC ₆ H ₁₃ 92.3 161-162

C ₁₉ H ₂₅ N ₂ O ₂ P 3 nC ₇ H ₁₅ 93.8 166-167 (chloroform-heptane)

C ₂ OH ₂₇ N ₂ O ₂ P four HC ₉ N ₁₉ 91.4 155-156

C ₂₂ H ₃₁ N ₂ O ₂ P 5 nC ₁₀ H ₂₁ 90.9 148-150 (chloroform-heptane)

C ₂₃ H ₃₃ N ₂ O ₂ P

Claims (1)

A method of producing N-diphenylphosphoryl-N'-alkyl (C ₆ -C ₁₀ ) urea by reacting diphenylphosphinic acid chloride with sodium cyanoacid in a solution of acetonitrile in the presence of magnesium chloride as a catalyst, followed by reacting the obtained diphenylphosphoryl isocyanate with n-alkylamines at room temperature solvent, characterized in that pre-diphenylchlorophosphine is oxidized with sulfuryl chloride at a temperature of 20-25 ° C in an environment of carbon tetrachloride to obtain the original chloro diphenylphosphinic acid hydride, the interaction of diphenylphosphinic acid chloride with sodium cyanate is carried out at a temperature of 20-25 ° C, and acetonitrile is used as a solvent in the interaction of diphenylphosphorylisocyanate with n-alkylamines.