JPH0357100B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to biscycloheptatrieno-tetraaza-dioxa or dithia-cycloalkenes and salts thereof useful as metal chelating agents.

Conventionally, many metal chelating agents have been developed to remove heavy metals from waste liquids, detoxify or remove heavy metals from the human body, or recover useful metals such as uranium from seawater.

From this viewpoint, as a result of intensive research, the present inventors have discovered biscycloheptatrieno-tetraaza-dioxa or dithia-cycloalkene, which are useful as metal chelating agents.

The present inventors previously discovered a 2-alkylaminotroponimine dimer represented by the following general formula [1] as a useful chelating agent.
With the aim of imparting further metal selectivity to these compounds, the present compound was invented after extensive research.

Here, K and l each represent an integer of 10 or less.

Compared to the compound of general formula [1] above, the compound of the present invention is expected to highly selectively form complexes with metals that easily form hexacoordinate complexes, such as cobalt, chromium, iron, etc. .

The compound of the present invention is represented by the following general formula [2].

Here, A represents oxygen or sulfur, and m, m', n, and n' each represent an integer from 2 to 4. In addition, salts include acids that bind to amino or imino groups under normal conditions, such as salts of inorganic acids such as hydrochloride, hydrobromide, sulfate, and nitrate, and salts of organic acids such as acetate. It refers to the salt of

The synthesis methods and physical properties of some representative compounds are shown below.

Abiscycloheptatrieno [7,1-b,
7,1-k]-1,4,10,13-tetraaza-
7,16-dioxa-cyclooctadeca-1,10
−Diene N,N'-di-(2-troponyl)-3-oxa-1,5-diaminopetane (1036mg, 3.32m
mole) and hexamethylphosphoramide (1528
mg, 8.53 mm mole) and chloroform (40 ml)
To this was added triethyloxonium fluoroborate (1519 mg, 8.40 mmole) dissolved in chloroform (10 ml). After heating under reflux for 16.5 hours, the reaction mixture was extracted with water.

The aqueous layer was washed with chloroform, made alkaline with 5% sodium carbonate, extracted with chloroform, and dried over potassium carbonate. The brown oil (1.50 g) obtained by distilling off the solvent under reduced pressure was dissolved in ethanol (300 ml), and 3-oxa-1,5-
Diaminopentane (600 mg, 5.76 mmle) was dissolved in ethanol (100 ml) and added dropwise over 5 hours.

After stirring overnight, the precipitated yellow solid was collected by filtration (463
mg), which was dissolved in chloroform and chromatofiltered through alumina (5 g), resulting in a yellow solid (460 mg).
I got it. Furthermore, the filtrate was concentrated and alumina (15g)
A yellow solid (124 mg) was obtained from the benzene/chloroform (0-50%) fraction by chromatographic separation.
I got it. The obtained solids were combined and chloroform/
Recrystallized from ethanol to give yellow needle crystals (516mg,
Yield: 41%).

Physical properties Melting point 223.0-229.5℃ (decomposition) ^1H -NMR (CDCl ₃ , δ value) 6.77 (4H, dd J=11.0, 9.5Hz) 6.24 (4H, d J=11.0, Hz) 6.14 (2H, t J= 9.5 Hz) 3.91 (8H, t J = 5 Hz) 3.49 (8H, t J = 5 Hz) ^13C -NMR 153.64, 133.07, 117.81,
110.35, 70.62, 46.70 IR (CHCl ₃ solution) 1595, 1510, 1470, 1130 cm ^-1 Elemental analysis C ₂₂ H ₂₈ N ₄ O ₂ Theoretical value C: 69.44, H: 7.42, N: 14.73 Actual value C: 69.40, H :7.41, N:14.60 I biscycloheptatrieno [7,1-b,
7,1-k]-1,4,10,13-tetraaza-
7,16-dithia-cyclooctadeca-1,10-
Dien N,N'-di-(2-troponyl)-3-thia-1,5-diaminopentane (1028mg, 3.13m
mole) and hexamethylphosphoramide (1408
mg, 7.86 mmole) was dissolved in chloroform (40 ml), and a solution of triethyloxonium fluoroborate (1456 mg, 8.05 mmole) in chloroform (10 ml) was added.

After heating under reflux for 20 hours, the reaction mixture was extracted with water.
The aqueous layer was washed with chloroform, made alkaline with 5% sodium carbonate, extracted with chloroform, and dried over potassium carbonate. The orange oil (1364 mg) obtained by distilling off the solvent under reduced pressure was dissolved in ethanol (300 ml), and 3-thia-1,
5-diaminopentane (445mg, 3.70m mole)
An ethanol (100 ml) solution of was added dropwise over 4.5 hours. After stirring overnight, the resulting orange precipitate was collected by filtration (427 mg), dissolved in chloroform, and chromatofiltered through alumina (7 g). The obtained yellow solid (394 mg) was recrystallized from chloroform/ethanol to give yellow columnar crystals (320 mg,
25%) was obtained.

Physical properties Melting point 210℃ (decomposition) ^1H -NMR (CDCl ₃ , δ value) 6.60 (4H, dd J=10, 9Hz) 6.30 (4H, dJ=10 Hz) 6.19 (2H, tJ=9 Hz) 3.60 (8H, t J = 6 Hz) 3.12 (8H, t J = 6 Hz) ¹³ C-NMR 152.97, 133.34, 118.54, 110.76, 47.92,
33.39 IR (CHCl ₃ solution) 1595, 1510, 1462 cm ^-1 MS (M/Z) 412 (M ⁺ ) Elemental analysis C ₂₂ H ₂₈ N ₄ S ₂ Theoretical value C: 69.04, H: 6.84, N: 13.58 Experimental value C: 63.94, H: 6.83, N: 13.45

Claims (1)

[Scope of Claims] 1. Biscycloheptatrieno-tetraaza-dioxa or dithia-cycloalkene and salts thereof, represented by the following general formula. Here, A represents oxygen or sulfur, and m, m', n, and n' each represent an integer from 2 to 4.