PL233840B1 - Method for producing crystalline form of hydrate thiocyanate [di(2-amino-5-guanidine-pentane)(thiocyanate)copper(II)] complex - Google Patents

Description

The present invention relates to a process for the preparation of a crystalline form of the complex of thiocyanate hydrate [di (2-amino-5-guanidinopentane) (thiocyanate) copper (II)].

2-Amino-5-guanidinopentanoic acid, commonly called L-arginine, is a component of nonlinear optical materials (NLO) in optoelectronics (T. Prasanyaa, M. Haris, V. Jayaramakrishnan, M. Amgalan, V. Mathivanan, V. Phys. Ser. 88 (2013) 1). L-arginine is also one of the basic amino acids encoded by DNA, and copper (II) ion complexes such as [Cu (L-arg) 2] (NO3) 2 or [Cu (L-arg) (1,10-phenanthroline) Cl] · Cl are structural mimics of netropsin, an antibiotic that binds proliferatively to adenosine-thymine (AT) pair rich sequences and has both antitumor and antiviral activity. Both netropsin and L-arginine contain characteristic guanidine terminal groups, which are located in a small DNA groove (T. Leszczyński, H. Duński, Zeszyty Naukowe Politechniki Lodzkiej, 984 (2006) 65). The structural similarity of L-arginine to netropsicin causes that complex compounds of Cu ²⁺ ions with L-arginine also exhibit DNA binding efficiency (A. Patra, T. Bhowmick, S. Roy, S. Ramakumar, A. Chakravarty, Inorg. Chem. 48 (2009) 2932) and have been extensively studied for their intercalating and therefore anti-cancer properties.

The formula of the crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentano) (thiocyanato) copper (II)] is known from the publication of A. Wojciechowska, J. Janczak, A. Jarząb, W. Zierkiewicz, Acta of the International Symposium on Metal Complexes - ISMEC Acta, 5 (2015).

There is no known method of preparation of a crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentano) (copper (II) thiocyanate)].

The essence of the method for the preparation of the crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentane) (thiocyanate) copper (II)] of the formula 1 consists in the fact that one molar part of hydrated copper (II) chloride salt or sulfate (VI) salt ) copper (II) is dissolved in water and reacted with two parts by mole of 2-amino-5-guanidinopentanoic acid solution and two parts by mole of potassium thiocyanate salt solution, and after a minimum of 2-18 days, a crystalline form is obtained as the second product [di (2-amino-5-guanidinopentane) (thiocyanato) copper (II)] thiocyanate complex of formula 1.

Preferably, the molar ratio of the Cu ²⁺ : L-arginine: KSCN reagents is 1: 2: 2.

Preferably, the reaction is carried out on a magnetic stirrer with constant stirring.

The subject matter of the invention is illustrated in the examples, without limiting its scope. P r z k ł a d 1

The method of obtaining the crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentano) (thiocyanato) copper (II)] with the formula 1, [Cu (NCS) (L-arg) 2] · NCS · H 2 O.

CuCl2 · 2H2O salt, molar ratio of the reagents CuCl2: L-arginine: KSCN 1: 2: 2.

At room temperature, 0.1705 g (1.0 mmol) of copper (II) chloride dihydrate is dissolved in 10 cm ^{3 of} water, and then 0.3484 g (2.0 mmol) of 2-amino-5-guanidinopentanoic acid are dissolved in 10 cm ^{3 of} water. The aqueous solution of 2-amino-5-guanidinopentanoic acid is added dropwise with continuous stirring to the aqueous solution of copper (II) chloride. The resulting blue mixture is stirred on a magnetic stirrer for 15 minutes. The solution formed by dissolving 0.1944 g (2.0 mmol) of potassium thiocyanate in 10 cm ^{3 of} water is then added dropwise to the resulting mixture, with continued stirring. The mixture is allowed to evaporate slowly at room temperature. After 2-18 days, blue crystals of the [di (2-amino-5-guanidinopentane) (copper (II) thiocyanate)] thiocyanate complex of formula 1 are obtained as the second reaction product, which are filtered off and washed with water, and then dried for a long time. air at room temperature. The crystal structure is confirmed by X-ray structural analysis.

P r z k ł a d 2

The method of obtaining the crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentano) (thiocyanato) copper (II)] with the formula 1, [Cu (NCS) (L-arg) 2] · SCN · H 2 O.

CuSO4 · 5H2O salt, molar ratio of the reagents CuSO4: L-arginine: KSCN 1: 2: 2.

At room temperature, 0.250 g (1.0 mmol) of copper (II) sulphate pentahydrate is dissolved in 10 cm ^{3 of} water, then 0.3484 g (2.0 mmol) of 2-amino-5-guanidinopentanoic acid is dissolved in 10 cm ^{3 of} water. The aqueous solution of 2-amino-5-guanidinopentanoic acid is added dropwise with continuous stirring to the aqueous solution of copper (II) nitrate. The resulting blue mixture is stirred on a magnetic stirrer for 15 minutes. Then into the resulting mixture

PL 233 840 Β1 is added dropwise with constant stirring, the solution formed by dissolving 0.1944 g (2.0 mmol) of potassium thiocyanate in 10 cm ^{3 of} water. The mixture is allowed to evaporate slowly at room temperature. After 2-18 days, blue crystals of the [di (2-amino-5-guanidinopentane) (copper (II) thiocyanate)] thiocyanate complex of formula 1 are obtained as the second reaction product, which are filtered off and washed with water, and then dried for a long time. air at room temperature. The crystal structure is confirmed by X-ray structural analysis.

The FT-IR oscillation spectra for the crystalline form of the complex thiocyanate hydrate [di (2-amino-5-guanidinopentane) (thiocyanate) of copper (II)] and L-arginine are shown in diagram 1 - the most important positions of the bands for the complex thiocyanate hydrate [di (2- amino-5-guanidinopentano) (copper (II) thiocyanate)] and L-arginine are shown in Table 1 (positions of the bands in cm ^-1 ).

Graph 1

FT-IR oscillation spectra of the complex of thiocyanate hydrate [di (2-amino-5-guanidinopentano) (thiocyanate) of copper (II)], L-arginine and KSCN

Tall number [cnr ¹ j

Tabelal

The positions of the bands in the FT-IR and FIR (cm ^-1 ) spectrum of the thiocyanate hydrate [di (2-amino-5-guanidinopentano) (copper (II) thiocyanate)], L-arginine and KSCN complexes

KSC 2040 L-arginine 1720 1676 1616 1552 1377 Complex of formula 1 2077/2057 1645 1604 1583 1564 1388

Patent claims

A method for producing a crystalline form of copper (II) thiocyanate hydrate complex [di (2-amino-5-guanidinopentane) (thiocyanate)] of the formula 1, characterized in that one mole part of hydrated copper (II) chloride salt or sulfate salt ( VI) copper (II) is dissolved in water and reacted with two parts by mole of 2-amino-5-guanidinopentanoic acid solution and two parts by mole of potassium thiocyanate salt solution, and after a minimum of 2-18 days a crystalline form of the hydrate complex is obtained [di (2-Amino-5-guanidinopentane) (thiocyanate) copper (II)] thiocyanate of formula 1.

Claims (3)

A method for producing a crystalline form of copper (II) thiocyanate hydrate complex [di (2-amino-5-guanidinopentane) (thiocyanate)] of the formula 1, characterized in that one mole part of hydrated copper (II) chloride salt or sulfate salt ( VI) copper (II) is dissolved in water and reacted with two parts by mole of 2-amino-5-guanidinopentanoic acid solution and two parts by mole of potassium thiocyanate salt solution, and after a minimum of 2-18 days a crystalline form of the hydrate complex is obtained [di (2-Amino-5-guanidinopentane) (thiocyanate) copper (II)] thiocyanate of formula 1. 2. The method according to p. The process of claim 1, wherein the molar ratio of the Cu ²⁺ : L-arginine: KSCN reagents is 1: 2: 2. 3. The method according to p. The process of claim 1, wherein the reaction is carried out on a magnetic stirrer with continuous stirring.