SU537080A1 - The method of producing hydrochloride esters of aminoethylphosphonic acid - Google Patents

Description

one

The invention relates to the field of organophosphorus compounds and relates to a process for the preparation of new hydrochlorides of amidinoethylphosphonic acid esters of the general formula

(co) p., c (ta) lg-nC1 o

where R is alkyl,

which can be used as intermediates for the synthesis of phosphorus-containing 2-imidazolines, which are analogues of known surface-active agents for emulsification of water-oil lubricants, extraction of acid minerals from ores, emulsification of pesticides.

A known method of producing amidine hydrochlorides by reacting imino ether hydrochlorides of carboxylic acids with ammonia in ethyl alcohol in a closed vessel at room temperature 1. However, imino ester phosphorus hydrochlorides did not involve the compounds of the above general formula, their properties and method of their preparation were not described in the literature. and are new.

A method is proposed for the preparation of ester hydrochlorides, amidinoethylphosphonic acid, which consists in the interaction of 3-imino-3-alkoxypropylphosphonic acid hydrochloride with ammonia in an ethanol medium in a closed vessel at 10-15 ° C. Isolation of the target compounds is carried out

known techniques; the yield is 96-97%.

Carrying out the process at a temperature of less than 15 ° C is necessary to prevent the side reaction of amidation at the phosphorus atom, leading to a decrease in the yield of the target product.

The structure of the target compounds is confirmed by elemental analysis data, data of IR spectra, as well as the possibility of obtaining

of them are free esters of 2-amidinoethylphosphonic acid and their picrates.

In the IR spectra of the target compounds there are the following absorption bands: 1375 cm (P 0), 1310 cm- (C-N), 1040 cm-1 (P-O-

-C), 3300 cm-1 (-NHz).

Example 1. Preparation of 2-amidinoethylphosphonic acid diisobutyl ester hydrochloride.

A solution of 13.3 g (0.04 g-mol) of 3-imino-3-ethoxypropylphosphonic acid diisobutyl ester hydrochloride in 35 ml of absolute ethanol is placed in a vial, the vial is cooled to minus 40 ° C and a solution of 3.0 tons is added ( 0.18 g-mol) ammonia in 30 ml

Claims (2)

absolute ethanol. The vial is sealed and left at 10-15 ° C for 15 days. Thereafter, the vial is opened and the liquid is separated by filtration from a small amount of the resulting ammonium chloride. The solvent is removed from the filtrate under vacuum. The residue crystallizes. It is purified by reprecipitation with ethyl alcohol. 8.8 g (97%) of 2-amidinoethylphosphonic acid diisobutyl ester hydrochloride are obtained. The product is white crystals with mp. 153-155 ° С (with decomposition). Found,%; C 44.0; 43.95; H 8.70; 8.76; C1 11.82; 11.80; N 9.12; 9.36; R 9.95; 10.20. CiiHsfiCINaOgP. Calculated,%: C 43.92; H 8.73; C1 11.79; N9.32; R 10.30. When carrying out the process at 25 ° C, the yield of diisobutyl ester of 2-amidinoethylphosphonic acid hydrochloride is 30%, and at 50 ° C - less than 1%. The effect on the hydrochloride of an equimolar amount of sodium ethylate in absolute ethyl alcohol at 15–20 ° C with a yield of 97% gives 2-amidinoethylphosphonic acid diisobutyl ester as a yellow amorphous powder; charred without melting at 360 ° C in a sealed capillary. Found,%: C 50.00; H 9.50; R 11.61; N 10.52. SPNGZYGOZR. Calculated,%: C 49.98; H 9.55; P 11.72; . N 10.60. T. pl. picrata 166Example 2. Preparation of 2-amidinoethylphosphonic acid hydrochloride hydrochloride. As in Example 1, 13.7 g (0.05 g-mol) of 3-imino-Zethoxypropylphosphonic Acid dipropyl ester hydrochloride in 40 ml of absolute ethanol is reacted with 3.0 g (0.18 g-mol) of ammonia in 30 ml of absolute ethyl alcohol. After filtration of the reaction mixture and removal of the solvent in vacuo, the expected product is obtained in the form of a noncrystallizing viscous oil, the purification of which is carried out by resold with ether from chloroform. Exit 97%. Found,%: C 40.0 g, 39.76: H 8.07; 8,10; C1 12.9; 12.98; N 10.22; 10.20; R 11.40; 11.42. С9Н22С1М20зР. Calculated,%: C 39.63; H 8.5; C1 13.0; N 10.27; R 11.36. T. pl. picrate of dipropyl ester of 2-amidinoethylphosphonic acid 138-140 ° C. In the same manner, with the yield of 96%, 2-amidinoethylphosphonic acid diethyl ester hydrochloride is obtained. The product is a viscous oil. Found,%: C 34.60; 34.40; H 7.30; 7.35; C1 14.55; 14.50; : N 11.30; 41.35; P 12.50; 12.71. CrHis SSHRIN Calculated,%: C 34.36; H 7.43; C1 14.49; N 11.45; R 12.66. T. pl. picrate of 2-amidinoethylphosphonic acid diethyl ester 173 175 ° C. Similarly, 2-amidinoethylphosphonic acid diisopropyl ester hydrochloride is obtained in 97% yield. The product is a viscous oil. Found,%: C 39.8; 39.57; H 8.10; 8.21; C 13.1; 13.12; N 10.29; 10.23; R 11.23; 11.30. SdNggSSShzOZR. Calculated,%: C 39.63; H 8.5; C1 13.0; N 10.27; R 11.36. T. pl. picrate of diisopropyl ether 2 amidinoethylphosphonic acid 149-150 ° C. Claims The method of producing amidinoethylphosphonic acid ester hydrochlorides of the general formula (RO) iP CHiCHiC (HH) HK5. -Mx O where R is alkyl, characterized in that 3-imino-3-alkoxypropylphosphonic acid ester hydrochloride is reacted with ammonia in a closed vessel at 10-15 ° C. The source of information taken into account during the examination: 1. S. Djevassi, S. R. Scholz, Avyloxyacetaidines and 2 (-Avyloxymethyl) -imidazolines, I ACS, 69, 1688 (1947).