CS265796B1 - Copper coordination compounds and their method of preparation - Google Patents

Abstract

The invention relates to coordination compounds of the type N-salicylidene-α-aminoalkanoate-thiocyanatocopperates, of the general formula where M+ represents an alkali metal cation, cation [NH4j+, or some of its substituted derivatives [R4N]+ (R = alkyl, or aryl); TSB means the dianion of a three-donor Schifft base, derived from α-aminoalkanocarboxylic acid and salicylaldehyde, or its various derivatives substituted on the core, x = 0, 1, 2, 3; and a method for their preparation by reactions of N-salicylidene-n-aminoalkanoate copper complexes, of the composition [cu(TSB)l], or rCu2<TSB)2j (L = single-donor molecular ligand, including H2O) with the corresponding thiocyanato M+SCN". The final compounds have significant antimicrobial, especially fungicidal properties.

Description

The invention relates to copper (II) coordination compounds of the general formula

M ⁺ [Cu (TSB) (SCN)] - xH ₂ O wherein M ⁺ represents an alkali metal cation, Cn H 4] ⁺ , or one of its substituted derivatives of R 4 N ^{+ +} (R = alkyl, or aryl), TSB means dianlon of the three-donor Schlff base (O.CgH4 .CH = N.CR H.COO) ^ (r '= H, or alkyl) derived from one of the N-amino acids and salicylaldehyde, or its different aromatic nucleus substituted derivatives and ax = 0, 1, 2, or 3; as well as a process for preparing coordination compounds of this type.

Several copper compounds are known to be co-ordinated with dianions of the three-donor Schiff bases, [cu (TSB) 1] or £ cu ₂ (TSB) ₂ J. In the first case, Cu (II) co-ordinates another one-molecule molecular ligand besides dianion (TSB). (H ₂ O, pyridine-type N-ligands or pazoles, thiourea-type S-ligands, etc.). The second case involves two-core complexes in which one of the O-donor atoms (TSBs) is coordinated by a bridge.

Several of these coordination compounds have been studied as model compounds for biological systems, and some of them have shown remarkable antimicrobial activity in screening assays.

A disadvantage of these compounds in testing biological activity as well as in other applications is their limited, often negligible solubility in water and in polar organic solvents in general.

In the chemical literature have not been disclosed coordination compounds with the dianion of cupric tridentate Schiff bases of the type mentioned, the binding of a further anionic ligand SCN form a complex anion, as an ingredient in the composition of the water-soluble salts M ⁺ [^ Cu (TSB) (SCN) J ~ xH ₂ ABOUT.

The process for preparing the coordination compounds of the invention consists in reacting the corresponding starting compounds of the type [cu (TSB) 1], usually [Cu (TSB) (I ^ O)] or [Cu ₂ (TSB) ₂ J], where the abbreviations indicated are the same. as above, used as anhydrous compounds, or differently crystalline hydrates with excess M ⁺ SCN in just the right amount of solvent (water, methanol, ethanol, acetone) or mixtures thereof at temperatures of 25 to 80 ° C. Upon cooling of the filtered solutions, the compounds of the invention crystallize in good yields as crystalline, dark green-colored products of good purity.

The selected examples illustrate but do not limit the general method for preparing the compounds of the invention and characterize their composition, as well as some properties and effects. In addition to the yields, the determined content of elements (C, Η, N), the spectral characteristic in the solid state (nujol suspension technique), based on the position of the absorption band d-d transitions in the visible region, the antimicrobial activity against Escherichia coli,

Candida albicans, Microsporum gypseum Trichophyton terrestre, characterized -3 minimum inhibitory concentration (MIC _of ug.cm).

Example 1

A mixture of 0.08 moles of potassium thiocyanate and 0.02 moles of copper (II) hemihydrate, or tetrahydrate, or 0.01 mole of bis (N-salicylidene glycinate) dimenium complex is dissolved in 40 cm ^{@ 1 of} water at 60 ° C. From the filtered solution crystallizes out after the addition of ca 120 ¹ of ethanol and cooling to / ν'0 ° C final product as a dark blue-green-colored crystals, which were isolated by the frit washed with cold ethanol, then ether and dried at room temperature for free. The yield of potassium N-salicylidene-glycinate-thiocyanate-dihydrate is 86.2%.

Analysis. For C ^ HH ^ NN ^ /SuCl, M _r = 373.9, calculated / found: 32.12 / 32.24% C; 2.96 / 2.80% Hj

7.49 / 7.60% N. Electron Spectrum (VIS): ν = 16 460 cm ^-1 . MIC: 700, 60, 700, 100, 100.

Example 2

A mixture of 0.08 moles of potassium thiocyanate and 0.02 moles of N-salicylidene-D, L-α-alaninate (II) complex in the form of anhydrous compound or monohydrate is dissolved in a mixture of 70 cm of water and 10 ml of citric acid. of methanol at a temperature of / 60 ° C. ethanol and smoothing to / in ° C the final product, in the form of dark blue-green-colored crystals, which after isolation on a frit are washed with cold ethanol, then with ether and dried free at room temperature. The yield of potassium N-salicylidene-D, L-α-alaninate-thiocyanate is 79%.

Analysis. For ^c 9 ^H 9 ^N 2 ° 3 ^SCuK 'M *. = 351.9; calculated / found: 37.54 / 37.57% C; 2.58 / 2.66% H;

7.96 / 7.71% N. Electron Spectrum (VIS): ν = 16 380 cm ^-1 . MIC: 900, 200, 800, 90, 90.

ΠΙαΧ

Example 3

A mixture of 0.06 mole of potassium thiocyanate and 0.02 mole of N-salicylidene-D, L-valinate copper complex in the form of anhydrous compound or monohydrate is dissolved in 80 cm @ 2 of dilute ethanol (/ »65%) heated to < 70 ° C. The resulting product crystallizes from the filtered solution after cooling to 0 ° C in the form of dark blue-green-colored crystals which, after isolation on a frit, are washed with cold ethanol, then with ether and dried free at room temperature. The yield of potassium N-salicylidene-D, L-valinate-thiocyanate is 74%.

Analysis: for ^C 13 ^H 13 ^N 2 ^O 3 ^{SCuK ·} M _r = 379.9; calculated / found: 41.09 / 41.25% C; 3.45 / 3.68% H; 7.37 / 7.36% N. Electron Spectrum (VIS): _{ν max} = 16,385 cm \ MIC:. ^ · 1,000, 400,> 1,000,

200, 300.

Claims (2)

OBJECT OF THE INVENTION 1. Coordinating compounds of the general formula M ⁺ [cu (TSB) (SCN)] ^- .xH ₂ O where M ⁺ represents an alkali metal cation, optionally [nh 4] ⁺ , or one of its substituted derivatives [H] NJ ⁺ , where R = alkyl or aryl, TSB means dianion a triple donor Schiff base (O.CgH4.CH = N.CR'H.COO) wherein R '= H; alkyl derived from α-aminoalkanecarboxylic acid and salicylaldehyde, or its different aromatic nucleosubstituted derivatives ax = 0, 1, 2, 3. 2. The method of preparing compounds according to claim 1, characterized in that it is treated as an exit Additive any of koordinačnýoh meSnatých compound of the formula [Cu (TSB) lR xH ₂ O or [Cu ₂ (TSB) _{2 2} H wherein J.xH L denotes a single-donor molecular ligand, including H ₂ O, and the other general substituents are as defined above with M ⁺ SCN ^- in a molar ratio of 1: 1.5 to 1:20 in favor of M ⁺ SCN ^- in the amount of water, methanol, ethanol needed. , acetone, or a mixture of these solvents, at temperatures of 30 to 80 ° C.