SU771109A1 - 2-alkyl(aryl)2-oxo-1,3,4-trialkyl-1-azaphospholenes-4 as stationary phase for gas chromatography and their preparation method - Google Patents

Description

In a three-neck flask with a capacity of 250 ml, equipped with a mechanical stirrer, a thermometer and a dropping funnel, 25.4 g (0.2 g-small) of n-butylidene-C-butylamine are placed in 100 ml of absolute benzene and 13, 1 g (0.1 g-mol) of ethyldichlorophosphine. The temperature of the reaction mass rises to 30 ° C. At the end of the dropping, the reaction mixture is heated to 40-50 ° C and stirred for 2-3 hours, maintaining the desired temperature (at 20 ° C, the entrapment is continued for 4-5 hours), then cooled to 0 ° C and 9.2 g of mixture is slowly added dropwise ( 0.2 g mol) of ethyl alcohol (either methyl or propyl or butyl) and 20.2 g (0.2 mol) of triethylamine.

Stirring is continued for 3-4 hours. Maintaining, temperature is 30-40 ° C, then cooled to room temperature, the precipitate of triethylamine hydrochloride and butylamine salt (21.00 g) is filtered off, the benzene is removed from the filtrate and distilled. Fractions with the so-called boil, 105107 C at 0.05 mm Hg, st. Corresponds to the final product. Yield 13.1 (51%) dr 0.9674, h 1.4860, 3079, calculated 761300.

Found,%: C 65.63; 65.85; 65.34 H 10.84; 10.64; N 5.04; 5.14; R 11.94; 11.68,

Ci4H2eNOp

Calculated,%: C 65,398; H 10.889 N 5.44; P 12,044 ..

The IR spectrum of the obtained compound contains absorption bands; see characterizing groups (1205) C C () 1650, 3080) and PN-C (S) 1.480)

The NMR spectra of H 31p confirm the structure of the product. Cfp -60 ppm

Example 2 Preparation of 2-methy2-oxo-1-butyl-3-propyl-4-ethyl-1 aza-phosphonene-4.

7.6 g (0.06 gmol) of n-butylidene-N-butylamine and 3.5 g (0.03 gmol) of methyldichlorophosphine are obtained by the described method,

B.kip, 103-105 ° C at 0.08 mm

- Hg, Art., yield 3.5 g (49%), 0.9749

 G, 4859,, 5915, calc, 71,512.

Found,%: C 64.56; 63.95; H 10.60; 10.73; N 5.14 / 6.80; P 12.46; 12.88.

CiT,

, Calculated,%: C 64.22 .; H 10.69; : N 5.75; R 12.73. “G -55 m, D.

P i m e R 3. Preparation of 2-phenyl-2-ioxo-l-butyl-3-propyl-4-ethyl-azaphospholane-4.

Prepared analogously to example 1 of 12.7 g (0.1 g-mol) of H-butylide-N-butylamine and 8.9 (0.05 g-mol) of phenyldichlorophosphine.

T. Kip. 132-134 ° C, at 0.07 mmHg, yield 90 g (59%), 1.0434, 1.5295, MRj5 90.257, 9 1, 008,

Found,%: C, 70.60; 70.21; H 8.99; 9.11; N 4.70; 4.41.

P 9.73; 9.90.

Calculated,%: C, 70.84; H 9.17; N 4.58; R 10.14,

The molecular weight found by mass spectrometry is -305, calculated 305.168,

In the IR spectrum, (cm) S) 1210, (Р 0) - 1650, 3080, () il600 (arom. DRA)) 1480, (PN-C) d -47 ppm

5 Example 4, Preparation of 2-ethyl-2-oxo-1-butyl-3-ethyl-4-methyl-1-azaphosphonene-4.

Prepared analogously to example 1 from 19.8 g (0.15 g mol) of n-hophopyl Q den n-butylamine and 9.7 g (0.075 g mol) of ethyl dichlorophosphine,

T, kip. 115-120 ° C at 0.08 mmHg, yield 8.1 g (47%), diy 0.9936, p 1.4845, MR-66.084, calc, 66.894.

Found,%: C 62.73; 62.51;

H 10.30; 10.21; N 5.91; 5.75; P 13.01; 13.40,

. HW NOP,

Calculated,%: C, 62.84; H 10.56; N 6.10; R 13.50. c 59 ppm, 0 The synthesized compounds were tested as a stationary phase by gas chromatography. The test results are given in example 5,

P R and m e P 5, Sorbent, prepared on the basis of 2-alkyl- (or aryl) 2-OXO-1, 3,4-trialkyl-1-aza-phosphoroene-4.

It is deposited on a carrier of the mark hromosorb l) a fraction of 0.20-0.36 m in the amount of 15% by weight. The application is carried out in a solvent (absolute benzene) by evaporation while in a thermostat. After evaporation of the solvent, the resulting sorbent is loaded into a chromatographic column and, when conditioned, is conditioned for 5 hours,

It is then used to separate various organic substances, 0

To compare the sorption properties of the obtained sorbents with known ones, their chromatographic polarity factors are determined, which take into account the main types of molecular interactions of the stationary phase with the analyzed substances.

Benzene-x, ethanol-y, methyl ethyl ketone-z, nitromethane - and pyridine - S,

The table gives the factors for the polarity of the proposed stationary phase 5 in comparison with the known.

: i

Stationary phase

The structure of 2-ethyl-2-oxo-1-butyl-CH-3-PROPIL-4-ETHYL-2- (JjHsPC azaPhospholate-4o jj-2-phenyl-2-oxo-1-butyl-i-3) -propyl-2-azafosfelen-4 sHsPx. Tricresyl phosphate (CHjCjjH O) Po (standard)

i: TriJJ.jr: i JH-C-CrHv C -cijl S - I IrfH ° 0.80 5.14 2.74 2.61 3.22 1.74 3.22 2.58 4.14 2.95

These tables show that the claimed phase has an advantage over tricresyl phosphate in terms of the difference of polarity factors (xy), i.e. in the separation of aromatic hydrocarbons from hydroxyl compounds.

Claims (3)

Invention Formula 1, 2-alkyl (oryl) -2-OXO-1, 3,4-trialkyl-1-azafosfenene-4 of the general formula Bn-d-r R: And about N-CH R where R is metnl, ethyl or phenyl, R is ethyl or propyl. R is methyl or ethyl, R is butyl, as stationary phase for gas chromatography. 2. A method for producing 2-alkyl (aryl) -oxo-1,3, 4-trialkyl-1 azaphos olenov-4 according to claim 1, which consists in that azomethines are reacted with alkyl (aryl) dichlorophosphines in benzene followed by treatment with alcohol and triethylamine. j 3. The method according to claim 2, wherein the azomethines are reacted with alkyl (aryl) dichlorophosphines in a molar ratio of 2: 1 at 40-500s t. Sources of information taken into account in the examination 1. USSR author's certificate 249385,. CL, 07 F 9/40, 1968. 2. Yashin Ya.I. Physico-chemical basics of chromatographic separation. M., Himi, 1976, p. 135.