Methyl-aquacobyrinic acid, alkylation composition and method for detoxification of harmful compound using said composition

FIELD: chemistry.

SUBSTANCE: invention discloses an alkylation composition which is characterised by that it contains a cobalt complex, as well as a method for detoxification of a harmful compound, characterised by that a harmful compound containing at least one element selected from a group comprising arsenic, antimony and selenium is detoxified through alkylation in the presence of the disclosed composition.

EFFECT: obtaining novel compounds.

27 cl, 10 ex, 11 tbl

 

The technical field to which the invention relates.

This invention relates to the derived methyl-akvamarinovaya acid composition alkylation and method of detoxifying the harmful compound by utilizing the connection.

Prior art

Materials from heavy metals such as arsenic, antimony and selenium, are widely used as industrial materials, such as semiconductors, but the penetration into the environment they affect the body as a hazardous material for the body.

Previously as a way to remove these heavy metals used well-known way in which flocculate agent, such as polychlorinated aluminum (PHA)was added to waste water containing inorganic arsenic, such as harmful arsenic acid, and then after aggregation of inorganic arsenic sorbed on flocculosa agent and iron contained in the raw water and subsequently deposited, inorganic arsenic was removed by filtration, or the way in which arsenic compounds, etc. have absorbed using flocculonodular agent-based activated aluminum oxide, cerium.

On the other hand, it is known that in nature, inorganic arsenic is in the marine products such as marine algae, and that part of reorganize is anyone arsenic is transformed into the organic compound of arsenic, such as dimethyl-arsenic in physiological processes (Kaise et al. 1998, were obtained. Chem., 12 137-143). It is well known that this organic compound of arsenic is less toxic to mammals than inorganic arsenic. In particular, most of the arsenic in seafood exists in the form of arsenobetaine. It is recognized that arsenobetaine is a harmless substance.

The invention

In the above method of removing heavy metal, characterized by the use of filtration and absorption, it is necessary to store or recycle contaminated sediment containing harmful compound such as inorganic arsenic, and absorbent, which absorbed the harmful connection, for example, by isolating harmful compounds with concrete or other to prevent leakage into the environment. Thus, there is a problem of difficulty of a mass grave, because it takes the place of burial or a large space for processing space burial.

The objective of the invention is to solve the above problems by composition and method of detoxifying the harmful compound containing arsenic, etc. effectively and methodically through the application of specified composition.

The ways to solve problems

To solve these problems, the authors of this invention have conducted the intensity of the positive studies of the reaction of methylation harmful compounds, in particular, methylation, particularly demetilirovania more preferably elevation of the harmful compound containing arsenic, etc. through chemical reactions with the use of an organic complex of a metal having a relationship cobalt-carbon. I made this invention.

This complex is derived methyl-akvamarinovaya acid, which in accordance with this invention is characterized by having the following General formula (1):

In addition, the proposed composition for the alkylation according to the invention, in which the composition contains an organic complex of a metal having a relationship cobalt-carbon, and the organic complex of a metal is derived methyl-akvamarinovaya acid having the General formula (2):

Further, in the preferred embodiment of the composition for the alkylation according to the invention, an organic complex of a metal is methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4:

where X is CH3N or Na.

Further, in the preferred embodiment of the composition for the alkylation according to the invention harmful with the Association, containing at least one element selected from the group comprising arsenic, antimony and selenium, alkylate using organic complex of a metal.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the composition further comprises a reducing agent for recovering at least one metal selected from the group comprising arsenic, antimony and selenium.

Further, in the preferred embodiment of the composition for the alkylation according to the invention, the reducing agent is a material containing SH group.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the material has a SH-group, which is at least one selected from the group comprising glutathione, restored glutathione (GSH), cysteine, S-adenosyl-cysteine, sulforaphane, dithiothreitol, thioglycol.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the composition includes an metymirumi agent with S-Me group.

Further, in the preferred embodiment of the composition for the alkylation according to the invention incremental metymirumi agent represents at least one selected from the group including the cabbage soup methionine and S-adenosyl-methionine.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the composition contains a buffer solution.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the pH of the buffer solution is in the range of 5-10.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the composition contains an organic halide compound.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the organic halide compound is methyl-halide.

Further, in the preferred embodiment of the composition for the alkylation according to the invention of the methyl halide is at least one selected from the group comprising methyliodide, methyl bromide and methyl chloride.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the organic halide compound is a halogenated acetic acid.

Further, in the preferred embodiment of the composition for the alkylation according to the invention of the halogenated acetic acid is at least one selected from the group including Chloroacetic acid, brough the acetic acid and iodixanol acid.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the organic halide compound is at least one selected from the group comprising methyl chloride, methyl bromide, methyl iodide, Chloroacetic acid, bromoxynil acid, iodixanol acid, chloroethanol, bromoethanol, iodoethanol, chloropropionic acid, bromopropionic acid, iodopropionic acid, ethyl ester of Chloroacetic acid, ethyl ester bromoxynil acid, ethyl ester iodixanol acid.

Next, the method of detoxifying the harmful compound according to the invention, in which the harmful compound containing at least one element selected from the group comprising arsenic, antimony and selenium, detoxify by alkylation of harmful compounds in the presence of the composition in accordance with any of paragraphs 2-17.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention detoxification is achieved by increasing the degree of oxidation of the element.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention, at least one connection of one element alkylate.

Further, in the preferred embodiment ways is and detoxification of harmful compounds in accordance with this invention the element is arsenic.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention the dose leading to 50% lethal (LD50connections, detoxificating by alkylation, greater than or equal to 1000 mg/kg

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention the concentration leading to 50%inhibition of cell growth (IC50connections, detoxificating by alkylation, greater than or equal to 1000 microns.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention harmful compound selected from the group comprising arsenic trioxide, arsenic pentoxide, trichloride arsenic, pentachloride arsenic, arsenic sulfide compound, cyanide-arsenic compound, chloro-arsenic compound and other inorganic salts of arsenic.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention the alkylation represents methylation.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention harmful compound is transformed into dimethyl connection or trimethylene connect the tion by methylation.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention dimethyl connection represents dimethylaminoethanol (DMAE), dimethylarsinate (DMAA), dimethylarsonic acid or arsenosugar.

Further, in the preferred embodiment of the method of detoxifying the harmful compound according to the invention trimethylene connection is arsenocholine, arsenobetaine, trimethylarsine or trimethylsiloxy.

The composition for the alkylation according to the invention allows to achieve the effect, consisting in the possibility of alkylation harmful compounds, in particular the harmful compound containing arsenic, antimony and selenium, etc. easily and simply. In addition, the effect achieved by the method of the present invention is that it does not require a large space, such as storage location, and you can detoxify harmful connection without restrictions. Next, the effect is that does not form undesirable by-product, because the method does not apply to biological material in a viable state. Next, the effect achieved in accordance with this invention, is that you can reduce the content of harmful inorganic arsenic more than the simple method.

Brief description of drawings

Figure 1 shows the electronic spectrum of Co(III) complex of vitamin B12. (Solvent: methylene chloride). And shows (SP)2ob(III)7C1ether, and shows the case of [(CP)(H2O)Cob(III)7C1the ether]lO4respectively.

Figure 2 shows the electronic spectrum of Co(II) complex of vitamin B12. (Solvent: methylene chloride). And shows [b(II)7C1the ether]lO4(unsupported type), and shows [Cob(II)7C1the ether]lO4+ pyridine (basic type).

Figure 3 shows the electronic spectrum of the complex of vitamin B12. (Solvent: methylene chloride). On figa shows [(CH3)(H2O)Cob(III)7C1the ether]lO4(Solvent: methylene chloride, before exposure to light), and shows the range And after exposure to light.

Figure 4 shows HPLC-ICP-MS (high performance liquid chromatography with mass spectrometry with an induction-coupled plasma) chromatogram of the reaction product of methylation of inorganic arsenic with [(CH3)(H2O)Cob(III)7C1the ether]lO4. (A) shows the result after 30 minutes of reaction, (B) shows 4 hours after the reaction.

Figure 5 shows HPLC-ICP-MS chromatogram. No. on the graph corresponds to the number in table 3).

Figure 6 shows HPLC-ICP-MS chromatogram. No. on the graph corresponds to the number in the table is itzá 3).

7 shows changes in the concentration of arsenic compound in the reaction solution. (This corresponds No. 1-8 from table 3).

On Fig shows the change in the number of arsenic compounds (in %) in the reaction solution. (This is a graphical form No. 1-7 of table 3).

Figure 9 shows the change in the number of arsenic compounds (in %) in the reaction solution. (This is a graphical form No. 6-11 table 3).

Figure 10 shows a HPLC-ICP-MS chromatogram. No. on the graph corresponds to the number in table 4).

Figure 11 shows the HPLC-ICP-MS chromatogram. No. on the graph corresponds to the number in table 4).

On Fig shows HPLC-ICP-MS chromatogram (in the case of treatment with hydrogen peroxide). No. on the graph corresponds to the number in table 4).

On Fig shows HPLC-ICP-MS chromatogram (No. on the graph corresponds to No. 12-14 in table 4).

On Fig shows changes in the concentration of arsenic compound in the reaction solution (in case without treatment hydrogen peroxide).

On Fig shows changes in the concentration of arsenic compound in the reaction solution (after treatment with hydrogen peroxide).

On Fig shows the change in the number of arsenic compounds (in %) in the reaction solution (in case without treatment hydrogen peroxide).

On Fig shows the change in the number of arsenic compounds (in %) reacciona solution after treatment with hydrogen peroxide).

On Fig shows the change in the number of arsenic compounds (in %) in the reaction solution.

On Fig shows HPLC-ICP-MS chromatogram.

On Fig shows HPLC-ICP-MS chromatogram (corresponding to No. 10 in table 6, No. 10 in table 7 and No. 10 in table 8).

On Fig shows the electronic spectrum of methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4. A: before exposure, after exposure to light.

On Fig shows the electronic spectrum of methyl-akvamarinovaya acid sodium perchlorate [(CH3)(H2O)Cob(III)N]ClO4. A: before exposure, after exposure to light.

On Fig shows HPLC-ICP-MS chromatogram.

On Fig shown1H-NMR methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4.

On Fig shown1H-NMR signal in the case of the hydrolysis of methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]ClO4.

The implementation of the invention

Derived methyl-akvamarinovaya acid in accordance with this invention has the following General formula (4):

Further, in the composition for the alkylation according to the invention, where the composition contains organic the ski complex metal in relation cobalt-carbon, organic complex of a metal is derived methyl-akvamarinovaya acid having the General formula (5):

In a preferred embodiment X is H or Na. The reason why X is preferably H or Na was determined by the inventors is that you can turn trioxide arsenic, etc. in mid-arsenic, etc., with almost 100% yield in the methylation of arsenic, etc. because the use of such derivatives methyl-akvamarinovaya acid increases the solubility of the solution and increases concentration.

The inventors found that if the formula (5) X=H or Na, then the carboxyl group is more soluble compared to X=CH3(hydrophobic vitamin B12 (kobrinovo acid heptamethyl ether), which improves the solubility and provides a high concentration to improve the reaction efficiency of methylation.

On the other hand, in the case of hydrophobic vitamin B12 X=CH3in the formula (5), the connection can also be utilized as the connection has the following advantages (1), it can easily be extracted from the reaction mixture solution by using an organic solvent and re-process it, (2) reactivity in water-soluble system coexisting organic solvent t is aetsa greater than or equal to the reactivity of water-soluble vitamin 12 (methylcobalamin).

Further, in the preferred embodiment of the composition for the alkylation accordingly, this invention the composition contains methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7With1the ether]lO4formula 6], which is an organic complex of a metal containing cobalt-carbon bond:

The above compound can be used as the composition, although the connection where X=N, CH3or Na can be used as such. It can be used in combination with the same connection, for example, combinations of compounds, where X=N and where X=CH3, compounds where X=N and where X=Na, or compounds, where X=Na and where X=CH3or even compounds containing all possible compounds, i.e. compounds where X=N, where X=CH3and where X=Na.

That is, in the composition for the alkylation according to the invention it is possible to alkilirovanii harmful compound containing at least one element selected from the group comprising arsenic, antimony and selenium, with the use of an organic complex of a metal. The term "bad connection", as used here, means the connection providing any side effects on the body when the penetration into the environment and the effects on the body.

As harmful compounds containing the isiac, among the above-mentioned harmful compounds can be mentioned arsenous acid, arsenic pentoxide, trichloride arsenic, pentachloride of arsenic sulfide compound of arsenic, cyanide-arsenic compound, chloromelanite connection and other inorganic salts of arsenic and/or the like. In these arsenic compounds, for example, LD50(50% lethal dose for mice) is less than or equal to 20, which is toxic value for the organism.

Further, as a harmful compounds containing antimony, may be mentioned antimony trioxide, antimony pentoxide, trichloride antimony and pentachloride antimony and/or the like.

Further, as a harmful compounds containing selenium, may be referred to selenium dioxide, selenium trioxide.

In a preferred embodiment the composition of this invention may further contain a reducing agent for recovering at least one metal selected from the group comprising arsenic, antimony and selenium. The presence of a refreshing agent is additionally accelerates the alkylation. Although I believe that healing ability for arsenic or reaction transmediterranea likely regulated by the rate of conversion in arsenobetaine, turning in arsenobetaine etc. can be accelerated by adding such substances. As vosstanavlivajusa the agent may be mentioned, for example, a material having a SH group, for example, at least one material selected from the group comprising glutathione, restored glutathione (GSH), cysteine, S-adenosyl-cysteine, sulforaphane, dithiothreitol, thioglycol.

Further, in the preferred embodiment of the composition for the alkylation according to the invention the composition comprises an extension metymirumi agent with S-Me group. The presence of the additional factor meteorologi agent with S-Me group, makes it possible for a greater number of alkyl groups, and thus achieve a greater alkylation and consequently greater detoxification. As an extension meteorologi agent may be mentioned, at least one selected from the group comprising methionine and S-adenosyl-methionine.

Further, the composition for the alkylation according to the invention may contain a buffer solution. As the buffer solution can be applied solutions, which are usually used for separation, purification or conservation of biomedical materials. Without specific limitations can be mentioned buffer solutions such as Tris buffer, phosphate buffer, carbonate buffer and borate buffer. From the point of view of achieving a more secure detoxification pH buffer solution is preferably in the range is 5-10.

The composition for the alkylation according to the invention may contain an organic halide compound. From the point of view of making it easy, dimethyl compounds and/or trimethylene connection arsenobetaine, as the organic halide compounds may be mentioned methyl halide. From the viewpoint of high reactivity methylation as a methyl halide can be mentioned at least one selected from the group comprising methyliodide, methyl bromide and methyl chloride.

In addition, from the viewpoint of high reactivity alkylation, as the organic halide compounds may be mentioned at least one compound selected from the group comprising todokanu acid, iodoethanol, bromoxynil acid, bromoethanol, iodopropionic acid.

In the preferred embodiment of the organic halide compound may be halogenated acetic acid. As an example, halogenated acetic acids can be mentioned, at least one acid selected from the group including Chloroacetic acid, bromoxynil acid and Jodocus acid.

Further, in the preferred embodiment as an organic halide compounds may be mentioned at least one selected and the group, include methyl chloride, methyl bromide, methyliodide, Chloroacetic acid, bromoxynil acid, todokanu acid, chloroethanol, bromoethanol, iodoethanol, chloropropionic acid, bromopropionic acid, iodopropionic acid, Chloroacetic acid ethyl ester, bromoxynil acid ethyl ester and iodixanol acid ethyl ester.

Further disclosed a method of detoxifying compounds in accordance with this invention. The method of detoxifying the harmful compound according to the invention is characterized by the fact that the harmful compound containing at least one element selected from the group comprising arsenic, antimony and selenium, detoxify by alkylation of harmful compounds in the presence of the above-described composition for the alkylation according to the invention. The composition for the alkylation according to the invention and harmful compound used here, means those that are described above, and those, the disclosure of which may be used for the method for detoxifying a harmful compound in accordance with this invention.

In the preferred embodiment of the method of detoxifying the harmful compound according to the invention methoxytyramine connection has a concentration leading to 50% inhibition of cell growth is (IC 50), or the dose resulting in 50% lethal (LD50)more, i.e. it is possible to achieve greater detoxification, which is preferably carried out by increasing the degree of oxidation of the element contained in the above harmful connection. Specifically, it is possible to increase the oxidation state of one element by alkylation with the use of a composition of the present invention, as described above, as a catalyst for the reaction. It is preferable to turn the oxidation number three in oxidation number five in the case when the element is arsenic or antimony, and it is preferable to turn the oxidation number four in oxidation number six in the case of selenium.

In this invention the detoxification of harmful compounds carried out by alkylation. Detoxification of the present invention can be achieved by alkylation of at least one relationship of one element contained in the above harmful connection.

Specifically, it is possible to alkilirovanii at least one connection of one element by carrying out the reaction with the use of the composition for the alkylation of the present invention, as described above. As the alkyl group, is added to a single element, may be mentioned methyl group, ethyl group and through the group, etc. From the point of view of achieving the more effective detoxification a methyl group is preferred alkyl group.

In the method of detoxifying the harmful compound according to the invention from the point of view of safety for living organisms dose leading to 50% lethal (LD50) (oral toxicity, the corresponding lethal dose for 50% of mice), compounds, detoxifiying under the above alkylation, preferably greater than or equal to 1000 mg/kg, more preferably greater than or equal to 5000 mg/kg

Further, in the method of detoxifying the harmful compound according to the invention from the point of view of safety for living organisms concentration leading to 50% inhibition of cell growth (IC50), compounds, detoxifiying under the above alkylation or arilirovaniya, preferably greater than or equal to 1000 μm. The term "concentration leading to 50% inhibition of cell growth (IC50)"used here means a numerical value that yields the required concentration of a certain substance for blocking or inhibiting 50% of cell proliferation 100 cells. The smaller the numerical value IC50the higher cytotoxicity. Further, the IC50calculated according to the results of the evaluation of cytotoxicity, causing damage to plasmid DNA under conditions of 37°C. for 24 hours. On the config moment IC 50each arsenic compounds shown in table 1.

Table 1
The connection of arsenicIC50(mg/cm3)
1 As (III)0.0007
1 As (V)0.006
MMA1.2
DMA0.32
TMAO>10
AB>10
AC>10
Subject8
AS2

From table 1 it is evident that sugar arsenic (III)containing trivalent arsenic (III), has a higher cytotoxicity than monomethylarsonic arsenic (MMA) and demetilirovanny arsenic (DMA)containing pentavalent arsenic, but has a lower cytotoxicity than monomethylarsonic arsenic (MMA), demetilirovanny arsenic (DMA)containing trivalent arsenic, and arsenic acid. On the other hand, it is known that monomethylarsonic arsenic (MMA), Dimitri is consistent arsenic (DMA), containing trivalent arsenic, have higher cytotoxicity than arsenious acid (containing trivalent and pentavalent arsenic), but in General, compounds of arsenic (V) have greater security of living organisms from the point of view of cytotoxicity than the connection of arsenic (III).

LD50each arsenic compounds shown in table 2.

Table 2
The connection of arsenicLD50(g/kg)
I As(III)0.0345
As I (V)0.014~0.018
MMA1.8
DMA1.2
TMAO10.6
AB>10
AU6.5
Subject0.9

In the method of detoxifying the harmful compound according to the invention the time the biological half-life connections, detoxifiying the above alkylation, preferably less than or equal is about 8 hours. In the way of detoxifying compounds in accordance with this invention, it is preferable to transform the harmful compound in dimethyl connection or trimethylene connection through methylation because the compounds are safe and have a lower toxicity. As dimethyl compounds may be mentioned dimethylaminoethanol (DMAE), dimethylarsinate (DMAA), dimethylarsinate acid or arsenosugar. As trimethylene connection may be mentioned arsenocholine, arsenobetaine, trimethylarsine or trimethylsiloxy.

The implementation of the invention

The invention disclosed in detail with reference to examples, but the invention is not limited to the following examples. The following are the abbreviations used in the examples:

[(CH3)(H2O)Cob(III)7C1the ether]lO4: methyl-akvamarinovaya acid heptamethyl-ester perchlorate

iAs (III): trivalent inorganic arsenic

MMA: monomethylamine arsenic acid

DMA: dimitrievna arsenous acid

TMAO: trimethylsiloxy

AB: arsenobetaine (trimethylarsine-acetic acid)

DMAA: dimethylarsonic-acetic acid

AS: arsenosugar

Meso: methylcobalamin

GSH: glutathione (reduced form)

iSe (IV): inorganic selenium (chetyrehvet the th)

MIAA: Monastyrska acid

Synthesis of cobalt complex

Synthesis of [(CH3)(H2O)Cob(III)7C1the ether]lO4: methyl-akvamarinovaya acid heptamethyl-ester perchlorate

(1) Synthesis of (SP)2b(III)]7C1ether

The reaction scheme

The original substance is ciankobalamin, which turns into (JV)2Cob(III)7C1the ether.

The implementation of the experiment

1.0 g ciankobalamin (7,5×10-4mol) was dissolved in 300 ml of methanol and the resulting mixture containing 150 ml of methanol was added 50 ml of cold concentrated sulfuric acid followed by heating the mixture under reflux for 120 hours in the dark conditions in a nitrogen atmosphere. After that the reaction mixture are condensed under reduced pressure, and then was added 100 ml of cold water and neutralized with solid sodium carbonate. To the mixture was added 4.0 g of potassium cyanide (6.1×10-2mol) and was extracted with carbon tetrachloride (150 ml×3). Then extraction was performed with methylene chloride (150 ml×3). The above operation is carried out again, because the methylene chloride extract contained incomplete essential connection. Extract carbon tetrachloride was dried with sodium sulfate, and then dried at reduced pressure. Re-precipitation was carried out with benzene/n-hexane(1:1 V/V) to obtain a purple powder. (Received: 777 mg (7.1×10-4mol). Yield: 95%).

The result of the analysis

Melting point: 138-140°C, the Point of decomposition: 193-196°C. Electron spectrum shown in figure 1, a. IR-spectrum (analysis KBr): ν(C≡N)2130; ν(ester C=O), 1725 cm-1

Elemental analysis:

The actual measured value: C, 58.46; H, 6.74; N, 7.58 %

C54H73CoN6O14•H2O

Calculated value: C, 58.58; H, 6.83; N, 7.59 %

Figure 1 shows the electronic spectrum of Co(III) complex of vitamin B12. (Solvent: methylene chloride). And refers to (CN)2Cob(III)7C1ester, and [(CN)(H2O)Cob(III)7C1the ether]lO4.

(2) Synthesis of [(CP)(H2O)Cob(III)7C1the ether]ClO4

The reaction scheme

The starting material is (JV)2ob(III)7C1the ester, which is converted to [(CP)(H2O)Cob(III)7C1the ether]lO4.

The implementation of the experiment

50 mg (CN)2Cob(III)7C1ether (4.6×10-5mol) was dissolved in 100 ml of methylene chloride and stirred with 30% aqueous solution lO4in a separating funnel. The mixture was washed with water and dried with anhydrous sodium sulfate, and then dried under reduced pressure. They were re-precipitation with benzene/n-hexane to obtain a powder of red. (Received: 50 mg (3,9×10-5mol). Yield: 92%.

The results of the analysis

Melting point: 96-98°C, Point p is slorenia: 216-220°C. The electronic spectrum is shown in figure 1, C. the IR spectrum (analysis KBr): ν(C≡N)2150; ν(ether≡O)1730 cm-1

Elemental analysis:

The actual measured value: C, 53.75; H, 6.40; N, 6.03 %

With54H75SOP6O19

Calculated value: C, 53.92; H, 6.40; N, 5.93 %

(3) Synthesis of [Cob(II)7C1the ether]lO4

The reaction scheme

The original substance (CN)(H2O)Cob(III)7C1the ether becomes [Cob(II)Safir]ClO4.

The implementation of the experiment

50 mg (CN)(H2O)Cob(III)7C1ether (4,2×10-5mol) was dissolved in 100 ml of methanol and was wearisomely by blowing with nitrogen. To this mixture was added 400 mg of NaBH4(1.05 mol) to obtain the green color given With(I). To this mixture was added 3 ml of 60% aqueous solution of HClO4. Next was added 50 ml of water and extraction was performed with methylene chloride. The mixture was washed with water and dried with anhydrous sodium sulfate, and then dried under reduced pressure. The idea they were re-precipitation with benzene/n-hexane to obtain powder orange. (Received: 50 mg (3.7 x 10-5mol). Yield: 87%.

The results of the analysis

Melting point: 96-100°C, the Point of decomposition: 190°C. Electron spectrum shown in figure 2, A. the IR-spectrum (analysis KBr): ν(C≡N)2150; ν(ester C=O), 1725 cm-1; ν(ClO4-)1100, 620 cm-1

Elemental analysis:

The actual ismaren the e value: C, 54.68; H, 6.41; N, 5.00 %

C52H73CoN4O18

Calculated value: C, 54.95; H, 6.47; N, 4.93 %

(4-1) Synthesis of [(CH3)(H2O)Cob(III)7C1the ether]lO4

The reaction scheme

The original substance Cob(II)7C1the ether]lO4becomes [(CH3)(H2O)Cob(III)7C1the ether]ClO4.

The implementation of the experiment

30 mg [b(II)7C1the ether]lO4(2,6×10-5mol) was dissolved in 100 ml of methanol and was wearisomely by blowing with nitrogen. To this mixture was added 300 mg of NaBH4(0,788 mol) to obtain the green color given With(I). To the mixture was added 37 mg of CH3I (of 2.6×10-4mol) and was stirred for 5 minutes. Then added 2 ml of 60% aqueous solution of 60% lO4. Then add 50 ml of water and extracted with methylene chloride. The mixture is then washed with water and dried with anhydrous sodium sulfate, and then dried under reduced pressure. They were re-deposition of benzene/n-hexane to obtain powder orange [(CH3)(H2O)Cob(III)7C1the ether]lO4. The electronic spectrum is shown in figure 3 (A: before exposure to light. Q: after exposure to light). Synthesis of methyl complex is confirmed by the cleavage of a methyl group Co-IU when exposed to light.

(4-2) Synthesis of [(CH3)(H2O)Cob(III)7C1the ether]lO4

Osuwestvlenieaj.in

50 mg [Cob(II)7C1the ether]lO4(4,4×10-5mol) was dissolved in 30 ml of acetic acid, removing the oxygen by blowing with nitrogen. Then to the mixture was added 600 mg of powdered zinc and stirred in a stream of nitrogen for 10 minutes. After the color thus obtained solution changed to dark green in a dark place, thereto was added 1.0 g of CH3I (7,0×10-3mol) and was stirred for 5 minutes. After the reaction, the powder of the zinc was removed by filtration and added to the filtrate to 50 ml of 15% aqueous solution lO4. Carried out the extraction with methylene chloride (50 ml × three times). After extraction were washed in 5% (mass) of a solution of sodium bicarbonate and distilled water, and dried with anhydrous sodium sulfate, and then dried under reduced pressure. They were re-deposition of benzene/n-hexane to obtain powder orange, 43 mg (84%) of [(CH3)(H2O)Cob(III)7C1the ether]lO4.

The results of the analysis

IR spectrum analysis with KBR):ν(ester C=O)1730 cm-1; ν(ClO4-)1100, 620 cm-1

1H-NMR(CD3OD, TMS): δ-0.18 (3H, s, CH3-From)

Elemental analysis:

The actual measured value: C, 54.49; H, 6.61; N, 4.96 %

C53H78ClCoN4O19

Calculated value: C, 54.43; H, 6.72; N, 4.80 %

Figure 2 shows the electronic spectrum of Co(II) complex of vitamin b12(Solvent is: methylene chloride). And shows a case [Cob(II)7C1the ether]lO4(unsupported type), and In [b(II)7C1the ether]lO4+ pyridine (basic type). Figure 3 shows the electronic spectrum of the complex of vitamin B12(Solvent: methylene chloride). On figa shows [(CH3)(H2O)Cob(III)7C1the ether]lO4(Solvent: methylene chloride, before exposure to light), and shows the range And after exposure to light.

Example 1

The reaction scheme

The implementation of the response

1.5 ml tube type Eppendorf) was added 740 μl reaction buffer (100 mm Tris-Hcl (pH 7,8). To it was added 220 μl of 100 mm aqueous solution of GSH and stirred apparatus Voltex within 30 seconds. Next was added 20 μl of a standard solution of inorganic selenium (Se) (IV) 1000 hours/million (atomic absorption). This solution was left for 60 minutes at 37°C. thereto was added 20 μl of a standard solution of inorganic arsenic (III) 100 hours/million (atomic absorption) and was stirred for 30 seconds. Thereto was added 20 μl of 7.4 mm methanolic solution of [(CH3)(H2O)b(III)7C1the ether]lO4(methyl-akvamarinovaya acid heptamethyl-ester perchlorate) (Composition A). The reaction was carried out in a bath while maintaining a constant temperature of 37°C, estimating the increase in the amount of product produced by sampling with the reg is popular intervals.

Analysis of the product

Qualitative and quantitative analysis was performed by applying ion mass spectroscope with induction-coupled plasma (Agilent 7500ce), directly associated with high-performance liquid chromatograph (Agilent 1100) online with a retention time of the standard sample when compared with the reaction product. Figure 4 shows HPLC-ICP-MS chromatograms.

(4) Conditions analysis

As a standard sample of organic arsenic was used MMA, DMA, TMA, Theme, AB and AC, which is commercially available reagents from Optronics Co., Ltd. (Trichemical Research Institute), and as a standard sample inorganic arsenic was used sodium salt As(III), As(V), which is commercially available high grade reagent from Wako Pure Chemical Industries, Ltd. Standard solution 100 mg/100 ml of each of the arsenic compounds were prepared by dilution in ultrapure water (Millipore).

Working conditions ICP-MS instrument were as follows:

Power forward: 1.6 kV

Reflected power: <1V

The flow of carrier gas: AG 0,75 l/min

Sampling 8.5 mm

Monitoring of mass m/z=75 and 35, the internal standard m/Z=71

The duration of exposure 0.5 sec 0.01 sec

The scan time 1 time

Conditions of HPLC are as follows:

Eluent: 5 mm nitric acid/ 6 mm ammonium nitrate/ 1.5 mm pyridine-dicarboxylic acid

With the speed of the eluent flow: 0.4 ml/min

Injected volume: 20 ál L

Column: cation-exchange column Shodex RSpak NN-414 (150 mm×4.6 mm internal diameter)

The column temperature: 40°C

Figure 4 shows HPLC-ICP-MS chromatogram of methylated reaction product of inorganic arsenic, corresponding to the formula [(CH3)(H2O)Cob(III)7C1the ether]lO4. Curve (A) shows the result after 30 minutes reaction, and (C) after 4 hours after the reaction. As follows from figure 4, it is clear that harmful inorganic trivalent arsenic [iAs (III)] is transformed into MMA and DMA, having low toxicity, appropriate toxicity [(CH3)(H2O)b(III)7C1the ether]lO4.

Comparative example 1.

The experiment was performed in the same manner as in example 1 except for the addition of [(CH3)(H2O)Cob(III)7C1the ether]lO4(Composition). The analysis found that methylation has not occurred.

As shown in example 1, methylated arsenic (MMA) and demetilirovanny arsenic (DMA) was developed faster than in comparative example 1. In the presence of [(CH3)(H2O)Cob(III)7C1the ether]lO4observed a noticeable effect, namely, that harmful inorganic compound was detoxifications and turned into methylated arsenic and demetilirovanny arsenic, with low toxicity.

Example 2

1.5 ml of p is obliku type Eppendorf placed 8.6 mg methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH 3)(H2O)Cob(III)7C1the ether]lO4(compound of formula (1). To it was added 1 ml of ultrapure water (mol/cm) for dissolving methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)ob(III)7C1the ether]lO4(7.4 mmol/l) (Solution A). 1.5 ml tube type Eppendorf) was added to 30.7 mg glutathione (reduced form) and was dissolved in 1 ml of ultrapure water (100 mmol/l) (Solution B). Preparing an aqueous solution of the trioxide of arsenic (atomic absorption: 100 hours/million: as metal arsenic (Solution C). Preparing an aqueous solution of se acid (atomic absorption: 1000 hours/million: as metal selenium) (Solution D). Prepared buffer solution of 100 mmol/l Tris-Hcl (pH of 7.8, 0.01 mol/l, pH was determined with a solution of hydrochloric acid (Solution E). 1.5 ml tube type Eppendorf) was added 720 μl of solution E, 20 μl of solution C and 220 μl of solution D and left for 1 hour at 37°C. To the mixture was added 20 μl of solution a and 20 μl of the solution and the reaction was performed in a bath at a constant temperature of 37°C. table 3 shows the concentration of arsenic compounds in the reaction solution.

/tr>
Table 3
No.Time (h)Concentration (µmol/l)
As(III)As(V)MMA(III)MMA(V)DMA(V)Only
1030000030
20.518.9370.0271.8764.1891.29328.293
3114.3770.0091.9815.8161.99525.420
4212.9440.0053.2675.463166825.657
5411.5840.0243.819 5.9482.99925.645
6218.5390.2051.9698.9452.99524.796
7487.5090.3970.02910.8992.97123.333
in723.4510.0770.0004.9471.43716.856
9210.0004.3110.00013.9603.18520.748
10480.0004.3520.00013.1473.07720.299
11720.0003.2690.0009.0292.18113.752
* No. 1-8 without treatment with hydrogen peroxide, and No. 9-11 - after treatment with hydrogen peroxide

Qualitative and quantitative analysis was carried out using HPLC-ICP-MS method with sampling 50 μl of the product at regular intervals and with a tenfold dilution of samples of ultrapure water (No. 1-8 from table 3). Next, 50 μl of reaction solution was taken as a sample and was treated with 50 μl of an aqueous solution of hydrogen peroxide (at 37°C for 1 hour), was diluted ten times ultrapure water and analyzed the reaction product in the same way (No. 9-11 of table 3). HPLC-ICP-MS chromatogram is shown in figure 5 and 6. Changes in the concentration of arsenic compounds in the reaction solution is shown in Fig.7. The percentage of arsenic compounds in the composition shown in Fig and 9.

Further reaction conditions were as follows:

The concentration of the substrate: [As]=30 µmol/l

The concentration of artificial vitamin 12: [Mesa]=150 µmol/l

The concentration of glutathione (reduced form): [GSH]=22 mmol/l

The concentration of selenium: [Se]=760 µmol/l

Puff the RNA solution: 100 mm Tris-Hcl buffer solution (pH 7,8),

The reaction temperature: 37°C

Figure 5 shows HPLC-ICP-MS chromatogram (No. on the graph corresponds to the number in table 3). Figure 6 shows HPLC-ICP-MS chromatogram (No. on the graph corresponds to the number in table 3). 7 shows changes in the concentration of arsenic compounds in the reaction solution (Graphical image # 1-8 from table 3). On Fig shows the change in the concentration of arsenic compounds in the reaction solution (graphic No. 1-7 of table 3). Figure 9 shows the change in the concentration of arsenic compounds (%) in the reaction solution (graphical image # 6-11 of table 3).

Example 3

The experiment was performed in the same manner as in example 2, except that the first solution was added, and then the solution A. the reaction Products were collected at regular time intervals and analyzed by HPLC-ICP-MS. The samples shown in table 4, with the numbers 1-7 were diluted unchanged and analyzed. The samples shown in table 4, with numbers 8-14 were treated with hydrogen peroxide solution and analyzed, as shown in example 2. As can be seen from table 4 and figure 10-17,95% or more of inorganic arsenic was methylated.

Table 4
No.the time (h) Concentration (µmol/l)
As(V)MMA(V)MMA(III)As(III)DMA(V)Only
10.2500.183.8412.4804316.93
20.500.356.487.791.1415.76
3101.208.843.752.6016.39
4201.659.021.173.9215.77
5307.270.764.5115.56
6407.851.080.694.6114.22
72408.910.000.624.6314.16
80.252.0210.0900.741.8514.69
90.51.5310.8500.221.9614.55
1010.6110.6700.073-2614.61
1120.389.8600.034.4114.69
1230.369.3500.004.8214.53
1340.339.4800.004.9014.71
14240.419.5600.014.8814.85
*No. 1-7 without treatment with hydrogen peroxide, and No. 8-14 after treatment with hydrogen peroxide

Table 4 shows the concentration of arsenic compounds in the reaction solution. Figure 10 shows a HPLC-ICP-MS chromatogram (No. on the graph corresponds to the number in table 4). Figure 11 shows the HPLC-ICP-MS chromatogram (No. in g is the Afik corresponds No. in table 4). On Fig shows HPLC-ICP-MS chromatogram (in the case of treatment with hydrogen peroxide) (No. on the graph corresponds to the number in table 4). On Fig shows HPLC-ICP-MS chromatogram (No. on the graph corresponds to No. 12-14 in table 4). On Fig shows the change in the concentration of arsenic compounds in the reaction solution (without treatment with hydrogen peroxide). On Fig shows the change in the concentration of arsenic compounds in the reaction solution (after treatment with hydrogen peroxide). On Fig shows the change in the concentration of arsenic compounds (%) in the reaction solution (without treatment with hydrogen peroxide). On Fig shows the change in the concentration of arsenic compounds (%) in the reaction solution (after treatment with hydrogen peroxide).

Example 4

The experiment was performed in the same manner as in example 3, except that each sample were incubated for 1 hour at 37°C before the addition of solution a and solution C. As shown in table 5 and Fig was methylated 95% or more of inorganic arsenic. These results confirm the formation of trimethylsilanol arsenic (Fig). HPLC-ICP-MS chromatogram is shown in Fig. Table 5 shows the concentration of arsenic compounds in the reaction solution.

Table 5
No.Time (h)Concentration (µmol/l)
As(V)MMDMMA(III)As(III)DMATMAOOnly
10.00.307.860.1615.481.710.0625.57
21.00.0014.941.511.355.480.0323.31
324.00.009.376.861.546.070.1123.96
424+H2O20.4116.040.00 0.486.390.0323.35

On Fig shows the change in concentration of arsenic compounds (%) in the reaction solution. On Fig shows HPLC-ICP-MS chromatogram.

Next, we conducted an experiment adding different types of reducing agent in addition to (or instead of) to glutathione (GSH). In addition to glutathione (GSH) (or instead GSH) was carried out by adding cysteine (Cys), dithiothreitol (DTT) and thioglycolate (TG). Used dimethyl sulfoxide (DMSO) as a solvent for dissolving the artificial vitamin b 12 (hydrophobic 12), etc. and apply the solvent with a high boiling point (to prevent drying due to water evaporating at the reaction temperature of 100°C or higher).

First, 0.1 ml glass tube (with attached silicone tube) was added GSH (2 mg, 6.5 mmol), 0.5 mg methyl-akvamarinovaya acid heptamethyl-ester perchlorate (0.4 mmol), ultrapure water (1 μl) (Tube with attached silicone tube was used to avoid evaporation of water).

To this mixture was added 1 μl of a standard solution of inorganic arsenic (atomic absorption, 5 hours/million in the form of arsenic), was placed in an oven heated to 130°C., and reaction was performed for 2 hours. The reaction product was diluted in the ten to thirty times with a 10% solution of hydrogen peroxide and analyzed using HPLC-ICP-MS (Sample NV).

Further experiments were performed in the same way with GSH, Cys, arsenic concentration and temperature were changed as shown in the table. The results are shown in tables 6-8. Table 6 shows the different types No. of samples using various reducing agents, table 7 shows the results of analysis of different types of samples using HPLC-ICP-MS (percent), while table 8 shows the results of analysis of different types of samples using HPLC-ICP-MS (concentration).

Table 6
No.SampleMesoGSH (mg)Cys (mg)DTT (mg)TG (mg)DMSO (ál)H2O (ál)Only
1NW120.00.01.00.01.02.0
2NW1 20.00.01.01.01.03.0
3NW0.520.00.01.00.01.02.0
4NW0.520.00.00.01.01.02.0
SNW0.520.00.00.01.01.02.0
inNW0.520.00.00.01.0 1.02.0
7NW0.502.00.00.01.01.06.9
8NW0.502.00.00.01.01.04.0
9NW0.502.00.00.01.01.018.5
10NW102.00.00.01.01.061.3
11NW1.5 02.00.00.01.01.06.3
12NW0.500.02.00.00.01.0#DIV/0
MeCo: Methylcobalamin GSH:Glutton (restored) Cys:Cysteine DTT: Danocrine TG:Thioglycolate acid DMSO:dimethyl Sulfoxide

Meso: methylcobalamin, GSH: glutathione (reduced form), Cys: cysteine, DTT: dithiothreitol (reducing agent), TG: thioglycol, DMSO: dimethyl sulfoxide.

Table 7
hours/million
NoSampleReaction time (h)The reaction temperature (°C)As(V)MMADMATMAOTeMAOnly
1NW21300.1540.0000.0721.1030.2811.610
2NW21300.2250.0860.1210.5430.7851.761
3NW21300.0520.0370.0880.5410.0450.762
4NW21300.0770.0350.0870.2330.0340.446
5HB582130 0.0800.0460.0640.4250.0380.654
6NW21300.0530.0950.2260.0460.0000.420
7NW21300.0370.0220.0720.5270.0460.703
8NW21300.0480.0910.1230.1780.0150.454
SNW21300.0130.0120.0130.088 0.0030.133
10NW21300.0060.0060.0100.1210.0160.158
11NW21300.0290.0160.0150.1170.0200.231
12NW21300.0090.0880.1570.1030.0120.814

Table 8
(%)
No.SampleReaction time (h)The reaction temperature (°C)As(V) MMADMATMAOSubjectOnly
1NW21309.60.04.568.517.4100
2NW213012.84.96.930.944.6100
3HB5621306.84.911.570.95.9100
4NW213017.37.914.952.27.6100
5HB58213012.37.19.865.05.8100
inNW213012.722.553.711.00.0100
7NW21305.233.210.274.96.5100
8HB67213010.619.927.039.23.3100
9HB682130 10.18.89.765.92.6100
10NW21303.63.66.176.89.9100
11NW213012.57.16.350.88.6100
12HB7121301.08.419.312.61.4100

Next, Fig shows HPLC-ICP-MS chromatogram (corresponding to No. 10 from table 6, No. 10 of table 7 and No. 10 of table 8). As shown in the HPLC-ICP-MS on Fig, trimethyl-arsine oxide, with low toxicity, was obtained as the main product in reacts the Onna mixture (77%).

Examples 5-10

Received various types of derivatives methyl-akvamarinovaya acid and studied their effectiveness.

Synthesis of methyl-akvamarinovaya acid sodium perchlorate [(CH3)(H2O)Cob(III)7ONa]lO4from methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4.

The reaction scheme

The starting material is methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4that turns into methyl-akvamarinovaya acid sodium perchlorate [(CH3)(H2O)Cob(III)7OONa]lO4.

Prepared six glass tubes, previously washed with 5% nitric acid. They were placed at 5 m (4.3 mmol) of hydrophobic vitamin B12. To it was added 10 μl of methanol, stirred, so that the hydrophobic vitamin B12was dissolved in methanol. To the solution was added 20 ml of 4 mol/l aqueous solution of sodium hydroxide were mixed, and the reaction was performed in a bath with controlled temperature maintained at 30°C for a predefined time. The reaction time was 1 hour (solution a-1, solution B-1), 4 hours (solution a-2 solution b-2)20 hours (solution a-3, solution b-3).

To acknowledge receipt of the derived methyl-akvamarinovaya to the slots have performed the following:

On Fig shows the electronic spectrum of methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4. And is the substance before exposure to light, and In substance after exposure to light. On Fig shows the electronic spectrum of methyl-akvamarinovaya acid sodium perchlorate [(CH3)(H2O)Cob(III)Na]lO4. And shows the substance before exposure to light, and In substance after exposure to light.

On Fig shows the absorption spectrum of methylated cobalt complex (A) before exposure to light. The spectrum of the cobalt complex (B), where a methyl group is separated after exposure to light. On the other hand, as can be seen in Fig, prior to exposure to the spectrum of the light absorption methylated cobalt complex (A), even if it is a complex formed by the reaction of alkaline hydrolysis. This confirms that Co-CH3the relationship persists after the reaction of alkaline hydrolysis, because after exposure to visible light range of the cobalt complex, where a methyl group is separated (In). Confirmation solubility methyl-akvamarinovaya acid sodium perchlorate in water after the reaction of alkaline hydrolysis was carried out as follows. The solvent was removed from the solution a-3 freeze-drying, the solution was dried. Added 50 μl of ultrapure the odes and stirred. The precipitate was not formed. On the other hand, although it was added 5 mg of hydrophobic vitamin b12{methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4} and 50 μl of ultrapure water and stirred, complete dissolution occurred. The above results clearly show that the methyl ester of hydrophobic vitamin b12{methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4} was cut in the reaction of alkaline hydrolysis and formed water-soluble methyl-akvamarinovaya acid sodium perchlorate [(CH3)(H2O)Cob(III)COONa]lO4. Electronic spectrum after exposure to light confirms that maintain a link With the-CH3required for methylation.

Results1H-NMR methyl-akvamarinovaya acid heptamethyl-ester perchlorate [(CH3)(H2O)Cob(III)7C1the ether]lO4shown in Fig. Identification using1H-NMR of the methyl group of [(CH3)(H2O)Cob(III)7C1the ether]lO4shown in No. 1-9. CH3the signal is directly related to the atom With that observed at -0,15 ppm proton seven methyl esters [(CH3)(H2O)Cob(III)7C1the ether]lO4gives seven signals between 3.5 ppm and 3.8 ppm1H-NMR signal after hydrolysis of the methyl-akvamarinovaya acids is heptamethyl-ester perchlorate [(CH 3)(H2O)Cob(III)7C1the ether]lO4shown in Fig. It is clear that the seven methyl-ester groups were hydrolyzed, since the proton signal seven methyl-ester groups [(CH3)(H2O)Cob(III)7C1the ether]lO4disappeared on Fig, while on Fig noted seven signals between 3.5 ppm and 3.8 ppm, respectively. It was found that the relationship With-not destroyed by alkaline hydrolysis, since there is a signal received from a methyl group, directly associated with the atom. Given the above, confirmed the conformation of [(CH3)(H2O)Cob(III)7Na]lO4(methyl-akvamarinovaya acid sodium perchlorate).

Preparation of the solution for the reaction of methylation of arsenic

Solutions a-1, a-2 and a-3 was neutralized with 6 mol/l aqueous solution of hydrochloric acid and 0.01 mol/l 1 mol/l sodium hydroxide solution so as not to exceed a total volume of 50 µl. It solutions In-1, b-2 and b-3 were added 20 μl of ultrapure water. In a test tube was added 20 mg (65 μmol) of reduced glutathione and stirred. Next was added 2 μl (2.7 nmol in the form of arsenic trioxide) solution of arsenic trioxide, which is trivalent inorganic arsenic (standard solution for atomic absorption 100 hours/million). Concentration in the reaction solution were as follows: glutathione (reduced form) (GSH): 1.3 mmol/l, hydro is savanna substance hydrophobic vitamin b 12(WSHB): 0,086 mmol/l of trivalent inorganic arsenic: 5 nmol/L. Conditions of preparation of the reaction agent shown in table 9. It was placed in a heater with a temperature equal to the temperature of the blood at a predetermined time. Reaction conditions shown in table 10.

Analysis

After the reaction, the reaction solution was treated with 10% hydrogen peroxide solution was diluted 500 times ultrapure water and conducted qualitative and quantitative analysis using the method of HPLC-ICP-Mbilo prepared 5 types of chemicals, namely, pentavalent arsenic, pentavalent monomethyl-arsenic (MMA), pentavalent dimethyl-arsenic (DMA), pentavalent trimethyl-arsenic (TMAO) and tetramethyl-arsenic (Theme). Using the standard model was built analytical curve and the quantitative definition. The relative concentration after the reaction was calculated using the following formulas.

The relative concentration of iAs (V)=100%×[iAs(V)/(iAs(V)+MMA+DMA+TMO+Theme)]

The relative concentration of MMA=100%×[MMA/(iAs(V)+MMA+DMA+TMO+Theme)]

The relative concentration of DMA=100%×[DMA/iAs(V)+MMA+DMA+TMO+Theme)]

The relative concentration of TMAO=100%×[TMAO/iAs(V)+MMA+DMA+TMO+Theme)]

The relative concentration Topic=100%×[Subject/iAs(V)+MMA+DMA+TMO+Theme)]

The release of arsenic (%) was calculated by the following formula.

Output=10%×(concentration of arsenic to the response/concentration of arsenic after the reaction)=100%×[iAs(III)/(iAs(V)+MMA+DMA+TMO+Theme)]

The results of example 5 (a-1), example 6 (a-2), example 7 (a-3), example 8 (1), example 9 (2), example 10 (b-3) shown in table 11. Table 9 shows the conditions of the hydrolysis of hydrophobic vitamin b12. Table 10 shows the reaction conditions. Table 11 shows the output (relative output, the absolute output) and the percentage of output.

Table 10
No.SolventTerms of cookingTo reactionReaction conditions
H2OThe reducing agentArsenic
GSHis(III)(100hours/million)iAs3The pace.Time
(ál)(mg)(ál)(h/million)(C)(h)
A-1-2041002
A-2-20241002
A-3-20241002
B-12020241002
B-22020241002
B-32020241002

Table 11
No.The result of anal is for
The product (output)The percentage yield
iAs5MMADMATMATeMAOnly
(h/million)(h/million)(cmln)(h/million)(cmln)(h/million)(%)
A-10.00.00.02.81.34.0101
A-20.00.00.03.60.33.997
A-30.00.00.03.90.34.1103
In-100 0.00.03.60.23.895
B-20.00.00.03.80.24.0101
B-30.00.00.03.90.14.099
No.The relative output
iAs5MMADMATMATeMAOnly
(%)(%)(%)(%)(%)(%)
A-100069 31100
A-2000828100
A-3000946100
In-100084in100
B-2000855100
B-3000891100
No.Absolute output
iAs5MMA DMATMATeMAOnly
%%(%)(%)%%
A-10006932101
A-200090797
A-3000977103
B-100089695
In-20005101
B-300098199

As shown in examples 1-5, arsenic trioxide selectively turned into trimethyl-arsenic (TMAO)with low toxicity. In particular, in examples 6-10 were obtained 90% or more relative output TMAO. Further, it was found that the conversion into water-soluble kourikova acid by hydrolysis of the methyl ester group of hydrophobic vitamin b12(kobrinovo acid heptamethyl-ether) makes it possible to improve the efficiency detoxifying treatment in accordance with the methylation reaction of toxic arsenic trioxide in aqueous solution.

On the other hand, in the case of hydrophobic vitamin b12, (X=CH3in the compound of formula (1), it was found that the compound (1) can easily be extracted with an organic solvent from a solution of the reaction mixture, and it is suitable for processing, (2) reactivity in water solution mixed with an organic solvent is equal to or larger than a water-soluble vitamin b12(methylcobalamine).

To the position of the present invention makes it possible to obtain more practical and industrially applicable method of detoxifying the harmful compound, arsenic, etc. This invention makes a significant contribution to the field of treatment of industrial waste, etc. and protection of the environment relating to contaminated sludge or soil, as innocuous compound, obtained by converting the harmful compound containing arsenic, etc. in a more innocuous compound by alkylation, is extremely stable and safe.

1. Derived methyl-akvamarinovaya acid having the following General formula (1):

2. The composition for the alkylation of harmful compounds containing at least one element selected from the group comprising arsenic, antimony or selenium, and the composition contains an organic complex of a metal having a relationship cobalt-carbon, which is derived methyl-akvamarinovaya acid, of General formula (2):

where X is CH3N or Na.

3. Composition for alkylation according to claim 2, in which the organic complex of a metal is methyl-akvamarinovaya acid heptamethyl-ester perchlorate [CH3)(H2O)Cob(III)7C1the ether]lO4General formula (3):

4. Composition for alkylation according to claim 2, which alkiliruet harmful compound containing at least one element selected from the group vkluchaya the arsenic, antimony and selenium.

5. Composition for alkylation according to claim 2, additionally containing a reducing agent for recovering at least one metal selected from the group comprising arsenic, antimony or selenium.

6. Composition for alkylation according to claim 5, in which the reducing agent is a material having a SH group.

7. Composition for alkylation according to claim 6, in which the material having SH group is at least one selected from the group comprising glutathione, restored glutathione (GSH), cysteine, S-adenosyl-cysteine, sulforaphane, dithiothreitol, thioglycol.

8. Composition for alkylation according to claim 2, additionally containing an extension agent methylation with S-Me group.

9. Composition for alkylation according to claim 8, in which the extension agent methylation is at least one selected from the group comprising methionine and S-adenosyl-methionine.

10. Composition for alkylation according to claim 2, additionally containing buffer solution.

11. Composition for alkylation according to claim 10, in which the pH of the buffer solution is in the range of 5-10.

12. Composition for alkylation according to claim 2 to 11, additionally containing organic halide compound.

13. The composition for the alkylation according to item 12, in which the organic halide compound is methylglucamide.

14. HDMI is required for alkylation according to item 13, in which methylguanosine is at least one selected from the group comprising methyliodide, methyl bromide and methyl chloride.

15. The composition for the alkylation according to item 12, in which the organic halide compound is a halogenated acetic acid.

16. The composition for the alkylation according to § 15, in which the halogenated acetic acid is at least one selected from the group including Chloroacetic acid, bromoxynil acid and Jodocus acid.

17. The composition for the alkylation according to item 12, in which the organic halide compound is at least one selected from the group comprising methyl chloride, methyl bromide, methyliodide, Chloroacetic acid, bromoxynil acid, todokanu acid, chloroethanol, bromoethanol, iodoethanol, chloropropionic acid, bromopropionic acid, iodopropionic acid, Chloroacetic acid ethyl ester, bromoxynil acid ethyl ester, iodixanol acid ethyl ester.

18. The method of detoxifying the harmful compound in which the harmful compound selected from the group consisting of inorganic compound of arsenic, antimony or selenium, detoxify by alkylation of harmful compounds in the presence of the composition according to any one of claim 2 to 17.

19. The method of detoxifying the harmful compound according p in which children is ificatio carried out by increasing the degree of oxidation of one element.

20. The method of detoxifying the harmful compound according p, in which at least one connection of one element alkylate.

21. The method of detoxifying the harmful compound according p in which the harmful compound is a compound of arsenic.

22. The method of detoxifying the harmful compound according p, in which the dose (LD50), leading to a 50% lethal compounds detoxificating by alkylation, greater than or equal to 1000 mg/kg

23. The method of detoxifying the harmful compound according p, in which the concentration leading to 50% inhibition of cell growth (IC50connections, detoxifiying by alkylation, greater than or equal to 1000 microns.

24. The method of detoxifying the harmful compound according p in which harmful compound selected from the group comprising arsenic trioxide, arsenic pentoxide, trichloride arsenic, pentachloride arsenic, mesaconitine connection, Cinematheque connection, chloromelanite connection and other inorganic salts of arsenic.

25. The method of detoxifying the harmful compound according to any one of p-23, in which the alkylation is methylation.

26. The method of detoxifying the harmful compound according A.25, in which the harmful compound is transformed into dimethyl connection or trimethylene connection by methylation.

27. The method of detoxifying the harmful connected to the I p, in which the dimethyl compound is dimethyl-Arsenal-ethanol (DMAE), dimethyl-Arsenal-acetate (DMAA), dimethylarsinic acid or arseno-sugar.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to stable complexes consisting of metal oxides - iron, cobalt or alloys thereof in form of nanoparticles and bifunctional compounds, where the bifunctional compounds are selected from thiols, carboxylic acids, hydroxamic acids, phosphoric esters or salts thereof, having an aliphatic chain containing a second functional group in the terminal position ω, which can be used in certain novel hydrophilic plates and fibres, as well as a method of producing complexes. The method involves reaction of dispersion of said nanoparticles in an organic solvent with a suitable binder. The mixture is stirred for several hours at low temperature and the obtained product is then cooled and separated by centrifuging, and can then be cleaned via repeated dispersion in a suitable solvent and repeated deposition.

EFFECT: novel complexes with improved solubility in water-alcohol medium are obtained.

13 cl, 3 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing bis(3,6-di(tert-butyl)benzosemiquinolates-1,2) of cobalt (II) or manganese (II) or nickel (II), of general formula: M(SQ)2 , where: SQ is 3,6-di(tert-butyl)benzoquinolate-1,2, and M = Mn(II) or Co(II) or Ni(II). The method is characterised by that a disubstituted salt of an alkali metal salt and 3,6-di(tert-butyl) pyrocatechol-1,2 is obtained, followed by reaction thereof with 3,6-di(tert-butyl)benzoquinoline-1,2. The formed 3,6-di(tert-butyl)benzosemiquinolate-1,2 of the alkali metal reacts with a Co(II) or Mn(II) or Ni(II) halide in an inert atmosphere in tetrahydrofuran.

EFFECT: simple synthesis of bis-semiquinolates of metals.

4 cl, 5 ex

FIELD: information technology.

SUBSTANCE: article with an image includes a substrate having a masked or concealed protective image on at least part thereof, which reflects less than 50% of radiation at wavelength 800-900 nm. The protective image contains an infrared radiation absorbing compound selected from:

or salt or polymer thereof, where M is a metal selected from iron, cobalt, nickel, aluminium, scandium, chromium, vanadium, titanium, manganese and lanthanide. R1 is selected from hydrogen, phosphonate, sulphonate, nitro, halogen, cyano, thiocyano, thioalkyl, thioaryl, alkyl, alkoxy, aryl, aryloxy, amine, substituted amines and substituted aryl. One of R2 and R3 is oxygen and the other is NO; n is a number corresponding to half the coordination number of metal M; each of L and L' independently denotes a ligand which forms a complex with metal M, and y is a number which corresponds to the coordination number of metal M. The infrared radiation absorbing compound does not form an intensely coloured protective image, and the protective image is pale, colourless or tinted. The invention also discloses a method of making the article with the image, using the compound and a method of authenticating the said article.

EFFECT: obtaining a protective image which can reflect less than half the light at 800-900 nm, and a protective image which is not intensely coloured.

14 cl, 35 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to novel derivatives of 1-allylimidazole with metal salts , where R denotes allyl, E denotes a metal, e.g. Zn (II) or Co (II), An denotes chlorine or acetate, n equals 2.

EFFECT: novel 1-allylimidazole derivatives having antihypoxic activity are obtained.

1 cl, 7 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: described is a novel compound - 1-acetyl-5,10-dioxy-5,10-dihydro-2H-anthra[2,3-D][1,2,3]triazole-7,8-dicarboxylic acid of formula , which can be used as a starting compound in synthesis of metal complexes of tetra[4,5]([6,7]1-acetyl-2H-naphtho[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanine.

EFFECT: possibility of use as dyes or catalysts.

1 cl, 3 ex, 4 dwg, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to tetra[4,5]([6,7]1-acetyl-2H-naphtho[2,3-D][1,2,3]triazole-5,8-dione)phthalocyanines of copper and cobalt of formula , where M denotes Cu and Co.

EFFECT: invention enables to obtain novel derivatives of phthalocyanines which can be used as dyes, as well as catalysts for various processes.

2 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-heptyloxy)anthraquinonoporphyrazines of copper and cobalt of formula .

EFFECT: obtained compounds can be used as dyes and catalysts.

4 ex, 5 dwg,

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-hydroxy)anthraquinonoporphyrazines of copper and cobalt of formula

.

EFFECT: compounds can be used as dyes and catalysts.

4 ex, 6 dwg

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of octa-4,5-carboxyphthalocyanine cobalt sodium salt, or 2,3,9,10,16,17,23,24-octacarboxylic acid of phthalocyanine cobalt (terephthal) of the formula (I) . Terephthal is a synthetic preparation used in catalytic ("dark") therapy of cancer based on generation of oxygen reactive species in tumor directly by chemical manner and in combination with ascorbic acid being without using the physical effect. Method for preparing octa-4,5-carboxyphthalocyanine cobalt sodium salt involves melting pyromellitic acid dianhydride with cobalt salt in the presence of urea followed by alkaline hydrolysis of prepared octa-4,5-carboxyphthalcyanine cobalt tetraimide. Salt formed after hydrolysis is purified from impurities, in particularly, from oligomeric compounds by column chromatography method on aluminum oxide, following precipitation of octacarboxylic acid, its, its washing out, concentrating and purifying from residual inorganic salts by washing out with distilled water and by neutralization with sodium hydroxide aqueous solution also, treatment with apyrogenic activated carbon, filtration and drying the end substance. Purification of octa-4,5-carboxyphthalocyanine cobalt from residual inorganic salt is carried out preferably by electrodialysis method after its partial neutralization to pH 5.2-5.5 at current density 0.15-0.25 A/dm2, temperature 20-35°C and the concentration 1.5-3.0% followed by complete neutralization to pH 8.7, treatment of obtained octacarboxy-PcCo salt solution with activated carbon, filtration and drying filtrate in a spray drier. Proposed method provides preparing octa-4,5-carbocyphthalocyanine cobalt salt of high purity degree and free of oligomeric compounds and residual chlorides.

EFFECT: improved method of synthesis.

5 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of platinum metal salts, in particular, palladium salts, namely, palladium (II) acetate. Method for synthesis of palladium (II) acetate involves dissolving metallic palladium in concentrated nitric acid, filtering and evaporation of palladium nitrate solution, its treatment with glacial acetic acid, filtration of formed sediment and its treatment with acetic acid ethyl ester and glacial acetic acid for its conversion to palladium (II) acetate followed by heating the prepared suspension for 6 h. Method provides preparing palladium (II) acetate with high yield in monophase state and without impurities of insoluble polymeric palladium (II) acetate.

EFFECT: improved method of synthesis.

3 cl, 2 tbl, 21 ex

Bioenergy complex // 2440308

FIELD: agriculture.

SUBSTANCE: process of anaerobic bacterial destruction of organic substances of biomass is carried out in a bioenergy complex. A bioenergy complex comprises a methane tank 3 with a coil 4, heat insulation 6, an auger mixing device 5, loading 7 and unloading nozzles, a gas holder 1, a heliocollector 11, an accumulator tank 9. The bioenergy complex is also equipped with a boiler of a water-circuit gas heating facility 8 for coolant heating, a wind-powered plant 14, a thermal electric heater 13 and a circulation pump 19 built into a pipeline 18 for reverse coolant supply.

EFFECT: invention makes it possible to increase efficiency and reliability of bioenergy complex operation under conditions of unavailability of centralised source of power.

1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to aerobic biological treatment of waste water and can be used in treatment plants of residential areas, agricultural and industrial companies. First, waste water is fed into a mechanical treatment device 1 for separation of solid residue, and then into a sand separator 2 and then further into a balancing tank 5 for balancing incoming waste water on concentration and water consumption. From the balancing tank 5, waste water is fed through a pipe 12 by a pump 32 into a primary settling tank 3. From the primary settling tank 3, waste water is fed through a pipe 13 into a biosorption tank 6. From the tank 6, waste water is fed through a pipe 14 into a biooxidation tank 7. Settling of the waste water and active sludge takes place in a secondary settling tank 4. Further, the treated waste water is fed into a post-treatment module 8 and then into a decontamination apparatus 9. The purified and decontaminated waste water is then output from the apparatus. Raw sludge and excess active sludge, separated after primary and secondary settling, are fed into an enzymatic-cavitational module 10 to obtain compound fertiliser.

EFFECT: invention increases efficiency and quality of treating waste water while simultaneously recycling raw sludge and active sludge by producing compound organomineral fertiliser therefrom.

5 cl, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to environmental protection, particularly to disinfection of waste water residue obtained during treatment of waste water on biological treatment plants. The method of detoxicating waste water residue involves treatment with a humin reagent taken in amount of 0.3-10.0 wt % per dry substance of the waste water residue, wherein the product of treating waste water residue with a humin reagent is further treated with a preparation of biologically active microorganisms, taken in amount of 0.05-1.00 l per ton of dry substance of the waste water residue. The product obtained using the disclosed method can be used as an organomineral fertiliser and insulation material on domestic and industrial waste dumping sites. Also disclosed is the capacity of biologically active microorganisms to not only disinfect waste water residue from pathogenic microflora and helminth eggs, but also participate in the process of disinfection from inorganic toxicants - heavy metal salts and organic toxicants - petroleum hydrocarbons, petroleum products and benz(a)pyrene.

EFFECT: high efficiency of the method of detoxicating waste water residue owing to stabilisation thereof, reduced content of inorganic and organic toxicants, as well as due to additional disinfection.

6 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to environmental protection, particularly to disinfection of waste water residue obtained during treatment of waste water on biological treatment plants. The method of detoxicating waste water residue involves treatment with a humin reagent taken in amount of 0.3-10.0 wt % per dry substance of the waste water residue, wherein the product of treating waste water residue with a humin reagent is further treated with a preparation of biologically active microorganisms, taken in amount of 0.05-1.00 l per ton of dry substance of the waste water residue. The product obtained using the disclosed method can be used as an organomineral fertiliser and insulation material on domestic and industrial waste dumping sites. Also disclosed is the capacity of biologically active microorganisms to not only disinfect waste water residue from pathogenic microflora and helminth eggs, but also participate in the process of disinfection from inorganic toxicants - heavy metal salts and organic toxicants - petroleum hydrocarbons, petroleum products and benz(a)pyrene.

EFFECT: high efficiency of the method of detoxicating waste water residue owing to stabilisation thereof, reduced content of inorganic and organic toxicants, as well as due to additional disinfection.

6 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: apparatus comprises: a tubular casing (2) having an inlet (4) for the product to be separated, an outlet (5) for the separated solid phase of the product, the liquid phase of which comes out through a filter wall (3) of the casing (2) and a transporting unit (7) inside the casing (2) for moving the solid phase to be packed to the outlet (5), and barrier element (9) at the outlet (5) for contact interaction with the product. In the initial position, the barrier element occupies at least part of the outlet opening of the outlet (5), and under the pushing force created by the packed product, can be elastically deformed to increase the size of the clearing hole of the outlet part. The barrier element (5) is formed by elements deviating from the periphery of the outlet opening of the outlet (5) to its centre and includes elements (11a) having a given degree of elasticity, which alternate with intermediate elements whose degree of elasticity differs from that of the main elements (11a), or alternate with incisions (11b).

EFFECT: invention enables to design a structurally simple and cheap device which is easy to maintain and repair.

5 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: compound method for reagentless treatment of waste water and briquetting sludge comprises two steps. The following operations are performed at the first step: distributed discharge of water into the receiving section of a settling tank in which suspended particles and immiscible liquids are separated according to density which is higher or lower than density of water, suspended particles and immiscible liquids with density higher than density of water accumulate and are held at the bottom of the settling tank; intense deposition of suspended particles and immiscible liquids with density higher than density of water at the bottom of the settling tank in the next sections; physical-electrical treatment in order to intensify deposition of dirt in series-arranged clarification tank lying on the length of the settling tank with mechanical offloading of the deposited sludge with a drag drainage conveyor into a mixture, where binder, filler and a neutraliser are added, and the sludge is stirred and pressed, and the obtained briquettes are disinfected in microwave ovens. The second step, which is realised using series-arranged devices, involves additional physical-electrical treatment of water, deposition of suspended particles, aeration and ozonation of water, collection of the sludge deposited in the devices, and said sludge is sent to the disinfection part of the drag conveyor.

EFFECT: method increases efficiency of treating waste water.

12 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to decontamination of household and industrial wastes used for production of organomineral fertilisers. Proposed method comprises subjecting effluents to high-rate vacuum pulses with the help of receiver and fast-operation valves, pulse duration not exceeding 1.0 s and pressure not exceeding 20 mm Hg to ensure required degree of decontamination.

EFFECT: accelerated and simplified procedure.

2 tbl

Bioreactor // 2427123

FIELD: agriculture.

SUBSTANCE: invention refers to agriculture and intended to produce biogas from biowastes of animal and poultry breeding of small- and average-size farms. Bioreactor includes housing in the form of steel tubular reservoir separated into three parts: loading, working and unloading parts with partitions - segments not reaching the reservoir bottom. Horizontal mixer offset from reservoir centre is installed inside working part connected to gas holder. At that, working part of tubular reservoir is divided into two sections: left and right ones with partition with a hole automatically opening and closing with gate valve with a float, depending on level of liquid fermenter contained in reservoir at unloading moment. End wall of right section of working part is equipped in addition with hot water tank.

EFFECT: simpler design of the present bioreactor allows increasing its capacity.

3 cl, 2 dwg

FIELD: agriculture.

SUBSTANCE: method includes detoxication of waste water residue with a humic reagent taken in amount from 0.3 wt % to 10.0 wt % per dry substance of waste water residue. Additionally the product of waste water residue detoxication with humic reagent is treated with a preparation of biologically active microorganisms taken in amount from 0.05 l to 1.00 l per ton of dry substance of waste water residue.

EFFECT: invention will make it possible to increase efficiency of method for production of organo-mineral fertiliser due to reduction of content of inorganic and organic toxicants in it, and due to their additional disinfection, to stabilise used residue of waste water, to eliminate rotting and unpleasant odour.

6 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to apparatus for neutralising and recycling highly concentrated organic wastes (deposits, sludge) arising from biological treatment of household waste water or waste water with similar composition. The apparatus for anaerobic processing of organic substrates into biogas and fertiliser has series-arranged collector of the initial substrate 1, hydrolysis apparatus 2, methane tank 6, effluent separator 13, thermal power unit for generating energy from biogas 22 and a boiler for burning solid hydrolysis wastes 17. The hydrolysis apparatus is fitted with an air bubbling device 3, between the methane tank and the effluent separator there is a floatation installation 9, the air bubbling device 10 of which, together with the air bubbling device of the hydrolysis apparatus, is connected to a compressor 19 with a gas-motor drive 20 operating on biogas, wherein the effluent separator 13 and the initial substrate collector are sealed, and their gas space, together the gas space of the hydrolysis apparatus and the floatation installation, is connected through a gas pipe to the gas boiler-recycler 16, which is in turn connected through a circulation line to the boiler for burning solid hydrolysis wastes, the gas-motor drive of the compressor and the thermal power unit for generating energy from biogas.

EFFECT: apparatus increases energy and environmental efficiency of the process of processing organic wastes into biogas and fertiliser.

1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to ecology, particularly, to clearing of soils contaminated by oil and oil products. Proposed method comprises washing contaminated soil by detergent fluid, its preparation using water and chemical agent, mixing said detergent fluid with soil to be cleared, mixing obtained suspension, settling it to remove floating oil contaminant and extracting the product of contaminated soil cleared by draining waste detergent fluid. To this end, said detergent fluid in every subsequent soil washing cycle is prepared from waste detergent fluid from previous cycle. For this, waster and chemical agent are added thereto to reach their initial content. Commercial mix of polyethylene glycol ethers of monoalkyl phenols is used as said chemical agent. After mixing detergent fluid with contaminated soil, obtained suspension is subjected to microware radiation and settled. After removal of floating oil contaminant from settled suspension surface and draining of waste detergent fluid, the extracted product of cleared contaminated soil is mixed with standard clean soil in amount that ensures tolerable concentration of oil contaminants in soil.

EFFECT: reduced consumption of detergent fluid, simplified process.

1 tbl, 3 ex

Up!