RU2372329C1 - Tris-substituted aminoguanidine derivatives, uses as analytical reagents - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and describes tris-substituted aminoguanidine derivatives of formula

, where:.

EFFECT: wider assortment of analytical reagents, used for detecting silver, copper and bismuth cations, and which can be used in analytical, pharmaceutical and chemical-toxicological practice.

2 tbl, 2 ex

Description

The invention relates to the field of search for new analytical reagents, namely, to the field of synthesis of compounds used to detect metal cations of s-, p- and d-elements.

In order to obtain analytical reagents with selectivity and high sensitivity with respect to transition metal cations, the interaction of triaminoguanidinium iodide with aliphatic, aromatic and mixed aldehydes and ketones, iodides of trisubstituted guanidine derivatives were synthesized, which were tested as analytical reagents for metal salts.

The experimental data showed that the obtained compounds in the environment of dimethylformamide with cations of silver, copper, bismuth form colored precipitates, namely:

N, N ', N' '- Tris (benzylidenamino) guanidinium iodide (compound I)

- with silver cations - light yellow, turning into dark brown;

- with copper cations - white;

- with bismuth cations - orange.

N, N ', N' '- Tris (butylideneamino) guanidinium iodide (compound II)

- with silver cations - brown;

- with copper cations - black-brown.

N, N ', N' '- tris (n-chlorophenylethyldenamino) guanidinium iodide (compound III)

- with silver cations - yellow, turning into dark brown;

- with copper cations - grassy green;

- with bismuth cations - yellow, gradually turning into orange.

N, N ', N' '- Tris (2-hydroxy-5-methoxybenzylideneamino) guanidinium iodide (compound IV)

- with silver cations - white;

- with copper cations - yellow-green.

N, N ', N' '- Tris (4-ethoxybenzylideneamino) guanidinium iodide (compound V)

- with silver cations - light yellow;

- with copper cations - white with a greenish tint;

- with bismuth cations - white.

N, N ', N' '- Tris (α-methylethylidenamino) guanidinium iodide (compound VI)

- with silver cations - yellow, turning into dark brown;

- with copper cations - black.

N, N ', N' '- Tris (C-methyl-4-chlorobenzylidene) guanidine (base, compound VII)

- with silver cations - white;

- with copper cations - blue;

- with bismuth cations - white.

N, N ', N' '- Tris (C-methylbenzylideneamino) guanidinium iodide (compound VIII)

- with silver cations - white, turning into red-brown;

- with copper cations - white.

N, N ', N' '- Tris (C-methyl-4-methoxybenzylidene) guanidinium iodide (compound IX)

- with silver cations - yellow, turning into brown;

- with copper cations - dirty green;

- with bismuth cations - yellow.

In addition, freshly prepared solutions of bismuth salts in an alcoholic medium form precipitations of white, yellow, and orange color with iodides of trisubstituted guanidine derivatives, namely:

- compound I is bright orange;

- compound II is orange-red;

- compound IV is light yellow;

- compound VI - bright orange;

- compound VII is white;

- compound VIII - orange;

- compound IX is orange.

For the studied cations, positive results were obtained with maximum dilution (table 2).

Production method

Example 1. Obtaining N, N ', N' '- tris (benzylidenamino) guinidinium iodide

2.32 g (0.01 mol) of triaminoguanidinium iodide are dissolved in a hot mixture of water (20 ml) and ethanol (30 ml). After cooling the solution to room temperature, a solution of 2.88 ml (d = 1.06) of benzaldehyde (0.03 mol) in 30 ml of ethanol is added dropwise, the reaction mixture is stirred and heated until the first portion of the precipitate appears. Stirring is continued at room temperature for 8-10 hours until complete precipitation. Recrystallization is carried out from a mixture of ethanol (90 ml) and water (40 ml) to obtain 3.87 g (78%) of N, N ', N' '- tris (benzylidenamino) guanidinium iodide (compound I) in the form of a light gray powder . Compounds II-IX are prepared in a similar manner (Table 1).

Example 2. Obtaining a colored complex of N, N ', N' '- tris (benzylidenamino) guanidinium iodide with bismuth cations

For experiments using a freshly prepared aqueous solution of bismuth nitrate with a content of 0.01 g Bi ³⁺ in 1 ml of solution.

a) To 1 ml of a solution of bismuth nitrate, with stirring, 4-5 drops of a 0.04% alcohol solution of N, N ', N' '- Tris (benzylidenamino) guanidinium iodide are added, an orange precipitate forms.

b) To 1 ml of a solution of bismuth nitrate, with stirring, 4-5 drops of a 0.04% solution of N, N ', N' '- tris (benzylidenamino) guanidinium iodide in dimethylformamide are added, an orange precipitate forms. By a similar method receive colored compounds II-IX with salts of silver, copper, bismuth (table 2).

INFORMATION SOURCES

1. I.M. Müller, R. Robson. Angew. Chem. Int. Ed. 2000. 39. No. 23, p. 4357-4359.

2. I.M. Müller, R. Robson, F. Separovie. Angew. Chem. Int. Ed. 2001. 40. No. 23, p. 4385-4386.

3. B.C. Sakov et al. DAN. 2003, t. 390, No. 5, p. 693-699.

4. K.N. Zelenin et al. ZhOKh, 1996, vol. 66, issue 1, pp. 141-146.

Claims (1)

Trisubstituted derivatives of aminoguanidine of the formula

Where
No. p / p R R ⁵ I Ph N II C ₃ H ₇ H III 4-Cl Ph CH ₃ IV 2-OH-5-OCH ₃ Ph N V 4-OC ₂ H ₅ Ph N VI CH ₃ CH ₃ VII 4-cl-ph CH ₃ (base) VIII Ph CH ₃ IX 4-OCH ₃ Ph CH ₃
used as analytical reagents.