CS271991B1 - Co-ordinating compounds of the cyano-N-salicylideneamino alkanoate type and their preparation. - Google Patents

Abstract

The solution relates to coordination compounds of the cyanate-N-salicylideneaminoalkanoate type of the general formula M[Cu(TSB)(OCN)] where M represents an alkali metal cation, or NH^ + and TSB means a dianion of a three-donor Schiff base derived from salicylaldehyde and <A-aminoalkanoic acid, or O-alanine, and a method of preparing N-salicylideneaminoalkanoate complexes of the formula [Cu(TSB)(H20)] . x H20, [Cu(TSB)23 . H20, or tCupSB>2(H20)] '. . x H20, where TSB means the same as mentioned above and x = 0, 0.5, 1, 2, 3, or 4 with alkali or ammonium cyanate in ethanol-water mixtures. The compounds have significant antimicrobial, especially fungicidal, properties.

Description

The invention relates to coordination compounds of the cyanato-N-salicylideneaminoalkanoatocopperates type, of the general formula I

M[Cu(TSB)(OCN)I (I), where M represents an alkali metal cation, or NH ₄ ⁺ and TSB denotes the dianion of the tridonor^j Schiff base, derived from salicylaldehyde and one of the <Z-aminoalkanoic acids, or B-alanine, of the formula /0-C6H4-CH=N-CHR-C00/ ^2- , or /0-C6H ₄ -CH=N-CH ₂ -CH ₂ .-C0D/ ² where R represents H, methyl, isopropyl or benzyl.

The compounds according to the invention are similar to coordination compounds of the type N-salicylidene-X^aminoalkanoato-thiocyanatocopperates /0.Krátsmér-šmogrovič, V. Seressová, C. Gážová, š. Varkonda and V.Konečný: Czechoslovak author's certificate no. 265796/ and N-salcylidene-β-alaninate-thiocyanatocopperates /J.Kratsmár-šmogrovič, 0.Švajlenová, š. Varkonda and V.Konečný: Czechoslovak author's certificate no. 270143/, differing, however, in that they coordinate as a monofunctional anionic ligand instead of SCN~ and OCN ^- particles.

In the professional literature, such metal compounds have not yet been described, which, by simultaneous coordination of dianions of the N-salicylideneaminoalkanoate type and OCN particles to the central atom, form complex anions cyanato-N-salicylideneaminoalkanoate metalates, representing a component of water-soluble salts of the composition m£Cu(TSB)(OCN)J.

The compounds according to the invention exhibit antimicrobial effects in in vitro experiments and are important as simple models of biological systems, e.g. metalloenzymes, while their biological activity in the performed experiments was comparable to, or even higher than, that of known compounds of the type M[Cu(TSB)(SCN)], or M ₂ [Cu(TSB)(SCN) ₂ ].

The method for preparing coordination compounds according to the invention consists in the reactions of N-salicylideneaminoalkanoate complexes of the general formula f.Cu(TSB) (H ₂ 0)J . x H ₂ 0, fCu ₂ (TSB). . x H ₂ 0, or ÍCu ₂ (TSB) ₂ (H ₂ 0)] . x H ₂ 0 where TSB represents the same as in the previous text and x represents 0, 0.5, 1, 2, 3 or 4, with an excess of the corresponding cyanate of the general formula M(OCN), where M represents the same as in the previous text, in mixtures of ethanol with water at temperatures of 40 to 70 ° C. After cooling the reacting systems, the coordination compounds according to the invention crystallize in good yields as green to blue-green colored products of very good purity.

Selected examples illustrate, but do not limit, the general method of preparation of the compounds according to the invention and characterize their composition, as well as some properties and effects. In addition to the yields, the results of elemental analysis, as well as the spectral characteristics of the preparations in the solid state, based on data on the position of the maximum absorption band of the dd-transitions, obtained by the Nujol suspension method, the examples also show the antimicrobial activity against Escherichia coli, Staphylococcus aureus, Candida albicans, Microsporum gypseum and Trichophyton terrestre resulting from the minimum inhibitory concentration of the individual preparations MIC |(ug.cm ^-3 j, determined by the dilution test method.

Example 1

2.7 g (0.01 mol) of (N-salicylideneglycinate)aquamate hemihydrate and 2.4 g (0.03 mol) of potassium cyanate are suspended in 180 m ³ of an ethanol-water mixture in a ratio of 2 : 1. The system is heated at 70 °C with constant stirring until the solid phase dissolves. The resulting solution is filtered while hot and allowed to cool to room temperature. The cured blue-green crystalline product is isolated, washed on a frit with ethanol and ether and dried in air. The yield of potassium cyanate-N-salicylideneglycinate is 70%. .

OS 271991 Bl

Analysis. For C _1Q H ₇ N ₂ O ₄ Cuk, M _r = 321.8 ; calculated/found: 37.32/37.52 % C ; 2.19/ /2.37 % H ; 8.70/8.69 % N. Electron spectrum (VIS) : =? = 15 280 cm~l . MIC : 800

IB 3 X J

300, > 1,000, 300, 90.

Example 2

2.8 g (0.01 mol) of hemihydrate (N-alicylidene-D,L-ch-alaninato)-aquamineral complex and 2.4 g (0.03 mol) of potassium cyanate are suspended in 50 cm ³ of a 1:1 ethanol-water mixture. The reaction system is heated at 60 °C with constant stirring until the solid phase dissolves. By following the procedure as in Example 1, the final product is obtained in the form of dark green crystals.

The yield of potassium cyanato-N-salicylidene-D,L-α-alaninate is 75%.

Analysis: For Ο^Η^Ν^^ΟυΚ, M _r = 335.8; calculated/found: 39.34/39.04% C;

2.70/2.95% H; 8.34/8.06% N. Electron spectrum (VIS): y ¹ _max = 16,320 cm ^- ·'· . MIC = f = 900, 200, 800, 90, 60.

Example 3 '

2.8 g (0.005 mol) of bis(N-salicylidene-D,L-valinate)dimethane complex and 2.4 g (0.03 mol) of potassium cyanate are suspended in 20 cm ³ of ethanol-water mixture (1:1). The system is heated at 60 °C with constant stirring until the solid phase dissolves. By following the procedure as in Example 1, the final product is obtained in the form of dark green crystals. The yield of potassium cyanate-N-salicylidene-D,L-valinate is 75%.

Analysis: For , M _r = 363.9 ; calculated/found: 42.91/42.62 % C;

3.60/3.68% H; 7.70/8.02% N. Electron spectrum (VIS): V _max = 15,200 cm ¹ . MIC = = >1000, 400, > 1000, 200, 200.

Example4 ·

In 60 cm ³ of ethanol, 5.45 g (0.01 mol) of aqua-bis(N-salicylidene-0-alaninate)dimethane complex monohydrate is suspended and a solution of 4.86 g (0.06 mol) of potassium cyanate in 20 cm ³ of water is added with stirring. A thick suspension is formed, which is heated with stirring in a water bath at 60 °C until the solid phase dissolves. The system is filtered while hot and allowed to cool to room temperature. The green crystals separated from the filtrate are washed with cold ethanol after suction on a frit and dried in air. The yield of potassium cyanate-N-salicylidene-0-alaninatemethanoate is 79%.

Analysis. For C^H^O^CuK, M _f = 335.8 ; calculated/found: 39.34/37.61 % C ; 2.70/2.64 % H ; 8.34/8.54 % N. Electron spectrum (VIS): v* _max = 14,000 cm ^-1 . MIC : : 700, 200, 700, 90.90.-

Claims (2)

OBJECT OF THE INVENTION 1. Coordinating compounds of the cyanato-N-salicylideneaminoalkanoate monanoate type of the general formula, M | Cu (TSB) (OCN) | (I), wherein M represents an alkali metal cation or NH ₄ ⁺ and TSB represents a dianion of a three-donor Schiff base derived from salicylaldehyde and o4-aminoalkanoic acid or Q-alanine, of formula / O-C6H4-CH = N-CHR-C00 / ^{2 -} , or / O-C6H ₄ -CH = N-CH ₂ CH ₂ COO / ² , where R denotes H, methyl, isopropyl or benzyl. 2. A process for the preparation of compounds of the formula I according to item 1, characterized in that the meonate compounds of the formula [Cu (TSB) (H2O _)] are reacted in a coordinated manner. x H ₂ 0, [Cu (TSB) ₂ 'J. x H ₂ O, or [Cu (TSB) ₂ (H ₂ O) 1. x H ₂ 0, where TSB means the same as in point 1 and x means 0, 0.5, 1, 2, 3, or 4, with alkaline or ammonium cyanate in a molar ratio of 1: 2 to 1: 8, in mixtures ethanol-water in a ratio of 1: 1 to 6: 1, at temperatures of 40 to 70 ° C.