Cobalt octasulfooctaphenyltetrapyrazinoporphyrazine

FIELD: chemistry of metalloorganic compounds, chemical industry.

SUBSTANCE: invention relates to preparing compounds of tetrapyrazinoporphyrazine order, namely, to cobalt octasulfooctaphenyltetrapyrazinoporphyrazine of the formula:

that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.

EFFECT: valuable properties of compound.

2 cl, 2 dwg, 4 ex

 

The invention relates to a new derived metallocarboxypeptidases. The inventive compound can be used as a catalyst in oxidation reactions of serosoderjaschei compounds, in particular thioureas, cysteine, and diethylamine.

The level of technology

Known compounds [D. Berezin, V. Klyuev., Korzhenevskogo A.B., " Izv. higher education institutions. Ser. Chemistry and chemical. the technologist. 1977. T.20. S-173], which are structural analogues of the claimed compounds - tetrapiridilporfina formula

where M=Zn, Cu, Co, Ni, Fe, and other

The metal complexes of tetrapiridilporfina used as effective catalysts of oxidation-reduction reactions, for example, in the oxidation of serosoderjaschei compounds [Maizlish V.E.; Klyvev V.N.; Korzhenevskii A.B. Metal complexes of tetrapyrazinoporphyrazines - effective catalysts of the oxidation of mercaptans. // Chem. Heterocycl. Compd. 1985. Vol.20. Iss.9. P.1031-1032]. However, because they do not possess solubility, it can only be used for heterogeneous catalysis.

The closest structural analogue of the claimed compounds [Kudrevich S.V., van Lier J.E. // Can. J. Chem. 1996. Vol.74 P.1718-1723. Halpern MG, Kudrevich SV; Novozhilova, I.G. // Chem. a heterocycle. connect. 1993. P.58-63] are the metal complexes of oktafeniltetrapirazinoporfirazina formula

where M=Mg, VO, (HO)2Si and other

One is to they have low solubility, therefore cannot be used as homogeneous catalysts.

Known homogeneous catalysts for initiating the oxidation of mercaptans and cysteine, but only in alkaline media and is not active as catalysts for the oxidation of diethylamine and thioureas oxygen [M. R. Tarasevich, Radyushkin K.A. Catalysis and electrolysis by metalloporphyrins. M.: Nauka, 1982, 168 S.]. Moreover, according to the structure they are not the closest structural analogue, as are derivatives of phthalocyanine.

Thus, no known connection tetrapiridilporfinov series, which catalyze the oxidation of serosoderjaschei compounds, in particular cysteine and thioureas, and diethylamine, and in acidic and neutral environments.

The invention

Inventive task consisted in finding connections tetrapiridilporfinov series, which would have a catalytic activity in oxidation reactions thioureas, cysteine and diethylamine in acidic and neutral environments.

The problem is solved by octachlorodibenzofuran cobalt formula

The structure of this compound proved by data of elemental analysis, electronic, and1H-NMR spectroscopy.

In the electronic absorption spectrum, which is typical for metal is the porphyrazine measured in water (figure 1), there is intense absorption in the region of 351 nm (band Sora) and 636 nm (Q-band).

In1H-NMR spectrum in the region of weak field 8.40-7.42 observed quadrouple corresponding to the signals of the protons of the phenyl fragments.

Octachlorodibenzofuran cobalt is a substance of a dark green colour and has a solubility in dimethylformamide, water, aqueous solutions of alkalis, concentrated sulfuric acid.

It has properties to catalyze the oxidation reaction of thioureas, cysteine and diethylamine in acidic and neutral environments.

Information confirming the possibility of carrying out the invention.

Octachlorodibenzofuran cobalt was obtained in the following way, implemented in three stages:

To implement the method using the following ingredients:

Benzyl - firm Arcos Organics

Diaminomaleonitrile firm Aldrich

Chlorosulfonic acid - GOST 2124-87

Cobalt (II) acetate - GOST 5861-79

Glacial acetic acid - GOST 19814-74

1 stage. Synthesis of 5,6-diphenyl-2,3-dicyanobenzene.

In a flask equipped with stirrer and reflux condenser, was placed 2.0 g (9.5 mmol) of benzyl, 1.0 g (9.5 mmol) of diaminomaleonitrile and 20 ml of glacial acetic acid. The reaction mass is allowed to stand 5 hours at a temperature instrumentation is of the reaction mass (about 120° C). After holding the reaction mass is then cooled, the precipitated precipitate is filtered off and washed on the filter with cold distilled water until neutral, dried at a temperature of 50-70°C.

The output of 5,6-diphenyl-2,3-dicyanobenzene 2.6 g (97.8%).

TPL=231-234°C.

Colorless substance, soluble in acetone, DMF.

IR-spectrum (PL. with KBr), νcm-1: 2240, 1617, 1513, 1447, 1377, 1203, 1072, 856.

1H-NMR spectrum (300 MHz, CDCl3), δ, ppm: 7.51-7.59 (hollows.), 7.43-7.48 (hollows), 7.35-7.42 (hollows).

13C-NMR spectrum (75 MHz, CDCl3), δ, ppm: 155, 134, 130, 129, 127, 112.

stage 2. Synthesis of oktafeniltetrapirazinoporfirazina cobalt.

In a quartz test tube is placed a mixture of 2 g (7.1 mmol) of 5,6-diphenyl-2,3-dicyanobenzene and 0.8 g (3.2 mmol) of cobalt acetate (II). The mixture is heated up to 250°C and maintained at this temperature for 20 minutes After cooling, the product is dissolved in 50 ml of concentrated sulfuric acid and precipitated by pouring into 200 ml of distilled water. The green precipitate is filtered off, washed with cold distilled water until neutral and dried. Cleaning is performed by washing with acetone to conventional Soxhlet extractions.

The output of oktafeniltetrapirazinoporfirazina cobalt (II) 1.40 g (66.0%).

Dark green substance has a solubility in dimethylformamide, of concentrated sulphuric acid.

Mass spectrum (field de is orble). 1254 (M+).

Found, %: C 70.13; N, 3.62; N 18.04 for C72H42N16About4Co.

Calculated, %: C 68.95; N, 3.38; N 17.87.

3 stage. Synthesis of octachlorodibenzofuran cobalt.

In a flask equipped with stirrer and reflux condenser, was placed 1.0 g (0.82 mmol) of oktafeniltetrapirazinoporfirazina cobalt and 5 ml of chlorosulfonic acid. The reaction mass is allowed to stand for 1 hour at boiling temperature (about 110°). After holding the reaction mass is then cooled and slowly poured with vigorous stirring to the cooled solution of sodium chloride (the temperature should not exceed 0-3°). The precipitation is filtered off and washed on the filter with cold distilled water until neutral. Received the green paste is heated to 100°and dried at this temperature. Hydrolyzed product is washed with concentrated hydrochloric acid, and dried. Purification of the synthesized complex was carried out using column chromatography. 0.1 g of the complex was dissolved in 2 ml of distilled water and was chromatographically twice: initially on a column with "Dowex" (eluent is water) and re - using gel chromatography (Molselect G9, eluent water). The final product was besieged from aqueous ethanol and dried under vacuum for 2 hours.

Output actualparameters is casinoportalen cobalt: 0.65 g (65.0%).

Dark green substance has a solubility in dimethylformamide, water, aqueous solutions of alkalis, concentrated sulfuric acid.

ESP in water: 351, 636 nm (figure 1).

Found, %: 46.76; H 2.42; N, 12.11; S 13.87. C72H44N16CoS8About24

Calculated, %: 47.19; N, 2.42; N, 12.23; S 14.00

The test of the claimed compounds as catalysts of oxidation reactions thioureas, cysteine, dimethylamine

Example 1. Using octachlorodibenzofuran cobalt in the oxidation of cysteine in a neutral environment.

A solution of 2 g of cysteine in 50 ml of 0.1M TRIS buffer to pH=7.0 and octachlorodibenzofuran cobalt in the amount of ˜10-4mol placed in a flask equipped with a bubbler and a mixer, and passed through the reaction mass of air at a temperature of 15-30°to change the color of the mass from purple to green. The precipitation of cystine filtered and washed with water. Obtain 1.87 g (94.4%) at pH=7. TPL 206-208.13With NMR (75 MHz 1% DCl in D2O) 170.48; 51.76; 36.25 (figure 2).

Example 2. Using octachlorodibenzofuran cobalt in the oxidation of cysteine in an acidic environment.

The method was carried out analogously to example 1, but as buffer used MES for pH=5.0.

Received 1.62 g (81.8%) cystine.

Example 3. Use actualparameters is casinoportalen cobalt in the oxidation of thiourea and dimethyltitanocene.

To 50 ml of water, add 2 g of the corresponding thiourea, then octachlorodibenzofuran cobalt in the amount of ˜10-4mol/L. Through the resulting mass bubbled air up until its color will change from purple to green. The precipitation is filtered off and washed with water. Receive, respectively, 0.83 g and 0.5 g (98.0%) of elemental sulfur. Mass spectrum (70 eV, electron impact) 256 (100%), calculated for S8- 256. Elemental analysis: Found S - 99.33%, the calculated S - 100%.

Example 4. Using octachlorodibenzofuran cobalt in oxidation reactions of diethylamine.

In 50 ml of diethylamine placed 0.05 g octachlorodibenzofuran cobalt and through the resulting solution was bubbled air under stirring for 4 hours at 15-25°C. Then the reaction mass is subjected to fractionation, fending off the first unreacted diethylamine, and then in the temperature range 117-120°With tetramethylpyrazine. Get 21.0% tetramethylpyrazine, which was analysed without further purification. The data of mass spectrometry (field desorption solution in methanol). 162 (M++H2O), 144 (M+).1H NMR (solution in CD3OD, 300 MHz), 2.89-2.94 (quadras. 8H, CH2), 1.28-1.25 (triple. 12H, CH3). 13C NMR (75 MHz, CD3OD) 41.9 (CH2), 12.4 (CH3).

About resulthavehectaresthetheinforprojecst cobalt formula



 

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