SU1081169A1 - N,n,n-tris(dioxyphosphorylmethyl-1,4,7-triazocyclononane) as complexone for selectively binding magnesium,zinc,copper and nickel cations - Google Patents

Abstract

N, N, S-Tris (dioxyphosphorylmethyl) -1,4,7-triazacyclononane of the formula HjOjPOHjN NCHjPOjHj C () VT (L as complexone for the selective binding of magnesium, zinc, copper, nickel cations.

Description

This invention relates to the chemistry of organic compounds of phosphorus with a CP bond, namely, the preparation of a new compound, NjN, M-tris (dioxyphosphorylmethyl) -1,4,7-triazacyclononane HgOjPCHgN with HNROZH3, which can be most effectively used as a comic, selective binding cations of metals are similar in properties. The specified compound, its properties and the method of preparation are not described in the literature. The nitrilotrimethylphosphonic acid N-oxide of the formula (CH2PO H) j, (II) which chelates magnesium ions is more effective than calcium ions l. However, the difference in the logarithms of the stability constants of the complexes was only 2.65, which is not enough for an analytical determination of one cation in the presence of another. Di- (aminoethyl) glycol ether-K, S, M, H-tetraacetic acid of the formula (HOOCCH) NCH CiLOCH CH AXIS CH N (22 2 11 jjj gives the maximum difference and known complexons in the stability constants of zinc and cadmium complexes ( 3.9 orders of magnitude 2 and 3j. The aim of the invention is to increase the effectiveness of complexones for the selective binding of metal cations of similar properties. The goal is achieved by a new compound N, N, N -tris (dio ciphosphoylmethyl) - 1,4,7 -triazacyclone nanom as a complexone for the selective binding of cations to Not even copper, nickel. A special feature of the complexone of formula I is its ability to form a complex with magnes for almost 5 orders of magnitude more stable than with calcium ions, as well as form a complex with zinc ions more stable than 5 orders, complex with cadmium. In this regard, the compound has no analogues among the complexones. The stability constant of the complex of the complexone of formula I with zinc is 10, which exceeds all known stability constants of the zinc complexates. New complexone N, N, N -tris (dioxyphosphorylmethyl) -1,4,7-triazacyclononane is obtained by the interaction of 1,4,7-triazacyclononane tribromhydrate with formalin and phosphorous acid in an acidic medium. Example. To a mixture of 3.7 g of 1,4, 7-triazacyclonone tribromhydrate, 2.5 g of phosphorous acid, 6 ml of water and 9 ml of concentrated hydrochloric acid heated to 120 ° C are added dropwise over 20 minutes 1.8 ml of aqueous formalin. The mixture is heated for another 2 hours at 120 ° C. In excess of HC1 in a water jet pump vacuum, the product is precipitated from the concentrated one. aqueous solution with acetone, recrystallized from water. 2.4 g of compound of formula I are obtained in a yield of 58%. Mp 245-247 ° C (decomp.). Found,%: C 26.4, H 6.2, N 10.2, N 10.2; R 21.9. .. Calculated,%: C 26.3, H 5.8; N 10.2; R 22.7. The NMR spectrum P n in water - a narrow singlet signal with a chemical shift of + 13 ppm relative to 85% phosphoric acid. The criterion for the selectivity of complexation of a complexone of the formula I is a high difference in the stability constants of the complexes that are similar in properties to the cations. The stability constants were found from the data on pH potentiometric titration in the system of a solution of the complexone of formula I (concentration 0.005 M) - metal nitrate (concentration 0.005 M) - KNOj (concentration 1.0 M) -. The total volume of the initial solution is 50 ml. Titration was carried out on a OR 208 pH meter (VNR) with an accuracy of ± 0.01 units. pH of KOH solution free of carbonates in a thermostatted cell at 25 ° C in a stream of argon. The obtained experimental data were used to calculate the stability constants of the complexes on the BESM-6 bJ computer. The results are presented in the table. 310 For sets of formulas I and II, the ionic strength (U 1.0, for other complexones. As follows from the obtained results, the proposed complexon exhibits a high selectivity of complex formation with respect to magnesium and zinc ions. The difference in logarithms 94 is the stability constants of the complexes with cations , is 4.6 and 5.2, respectively. The proposed complexone has a high efficiency of complexation with zinc, honey, nickel ions. All this allows it to be used for the selective binding of properties of meth allov.

N, N, M-tris (dioxyphosphorylmethyl) -1, 4,7-triazacyclononane formula I

N-Oxy nitrilotrimethylphosphonic

acid formula

II

Di (aminoethyl) glycol ether-N, N, N,

N-tetraacetic

acid of formula III

And and

1,4,7-Triazacyclononane 4jDiethylenetriamine-N, N, NN, N-pentamethylphosphonic acid 5

6.38 21.3

19.4 24.9

19.7

5.67

17,8

13.6

12.8

16.7 15.2 11.6 16.2

13.4

16.5

19.5

Claims (1)

Ν, Ν ', Ν' '- Tris (dioxiphosphorylmethyl) -1,4,7-triazacyclononane of the formula HzOjPCHjN 'ČSN ₂ PO ₅ N ₂ CHLH / CH ₂ PO5H ₂ as a complexon for the selective binding of cations of magnesium, zinc, copper, nickel.