Method of 2-methyl-1,4-napthoquinone obtaining

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining 2-ethyl-1,4-napthoquinone (menadione, vitamin K3), which is widely applied in medical practice and livestock breeding, especially in poultry breeding, as preparation for improvement of blood clotting. Method consists in oxidation of 2-methylnapthtaline with hexavalent chrome compounds in acid medium at heating. As compounds of hexavalent chrome applied is chrome-containing waste electrolyte with content of hexavalent chrome 150-500 g/l in terms of CrO3, which in form of mixture with sulfuric or acetous acid is slowly added to preliminarily heated to 35-40C 2-methylnaphtholine, and then temperature of reaction mass is increased to 70-90C.

EFFECT: obtaining target product with high conversion and higher output when using production wastes.

1 tbl, 10 ex

 

The invention relates to organic synthesis, and in particular to a method for producing 2-methyl-1,4-naphthoquinone (MNH, menadione, vitamin K3). MNH refers to the b vitamins, which are widely used in medical practice and animal husbandry, especially in poultry, as drugs to improve blood clotting.

It should be noted that in Russia vitamin K3not made, and all used based drugs are imported origin.

The most common methods of obtaining MNH based on the oxidation of 2-methylnaphthalene (MN) of different oxidants in the presence of catalysts and without them.

Among catalytic methods of oxidation include oxidation of MN tert-butylhydroperoxide dissolved in chlorobenzene, in the presence of a catalyst - tetrasulfonated iron fixed on the surface of mesoporous (MCM-41) and amorphous silicates (SiO2) [A.B. Sorokin, Alian Tuel. Heterogeneous oxidation of aromatic compounds catalyzed by metallophthalocyanine functionalized silicas // New J. Chem., 1999, 23, 473-476]. In this way the selectivity for MNCH does not exceed 34% conversion MN 90%.

Known methods of oxidation of MN by bichromate in the presence of compounds of ruthenium as catalysts [S.Chocron, M.Michman, Oxidation of 2-methylnaphthalene to 2-methyl-l,4-naphthoquinone with ammonium dichromate catalysed by RuCl3, Appl. Catal. 62 (1990) 119] and hydroinsulation presence of potassium in the AI porphyrins iron and manganese [R.Song, A.Sorokin, J.Bernadou, B.Meunier, Metalloporphyrin-Catalyzed Oxidation of 2-methylnaphthalene to vitamin K3and 6-methyl-1,4-naphtholquinone by potassium monopersulfate in aqueous solution, J. Org. Chem. 62 (1997) 673].

It is interesting to note that in Japanese [Shigekazu Yamazaki Chromium (VI) oxide-catalyzed oxidation of arenes with periodic acid // Tetrahedron Letters. 2001. V.42. P.3355-3357] the oxide of chromium (VI) already acts as a catalyst in the oxidation of MN orthogonal acid in acetonitrile to yield 64%.

Of great interest is the use of environmentally friendly and cheap oxidants, such as hydrogen peroxide.

You know the MN oxidation by hydrogen peroxide in acetic acid using iron salts (Fe(ClO4)3, (CH3Soo)3Fe) as a homogeneous catalyst [J.Kowalski, J.Ploszynska, A.Sobkowiak, Iron (III)-induced activation of hydrogen peroxide for oxidation of 2-methylnaphthalene in glacial acetic acid, Catal. Commun. 4 (2003) 603]. The selectivity of this process does not exceed 36% conversion of substrate 85-90%.

There is a method of MN oxidation by hydrogen peroxide using palladium (II)acetate, attached to the polystyrene-sulfonic resins as catalyst [S.Yamaguchi, M.Inone, S.Enomoto, Oxidation of 2-methylnaphthalene to 2-methyl-1,4-naphthoquinone with hydrogen peroxide in the presence of Pd(II)-polystyrene sulfonic acid resin, Chem. Lett. (1985) 827]. In this process, the selectivity for MNH reaches 66% conversion MN 90%.

It is also known the MN oxidation by hydrogen peroxide in the presence of titanium - and iron-containing molecular sieves (TS-1 Ti-Beta, Ti-NCL-1, Fe-Beta, Ti-MCM-41) [O.S.Anunziata, L.B.Pierella, A.R.Beltramone, Synthesis of menadione over selective oxidation zeolites, J. Mol. Catal. A: Chem. 149 (1999) 255; O.S.Anunziata, A.R.Beltramone, J.Cussa, Studies of Vitamin K3synthesis over Ti-containing mesoporous material, Appl. Catal. A: General 270 (2004) 77]. The maximum selectivity (54%) in the conversion of 22% was obtained for the Fe zeolite-Beta.

High catalytic activity in the oxidation of MN by hydrogen peroxide in the medium of acetic acid/acetic anhydride are complexes of rhenium, in particular methyltrioxorhenium (VII) (CH3Re3, Ito) [W.Adam, W.A.Herrmann, W.Lin, Ch.R.Saha-Moller, R.W.Fischer, J.D.G.Correia, Homogeneous catalytic oxidation of arenes and a new synthesis of vitamin K3, Angew. Chem. Int. Ed. 33 (1994) 2475; W.A.Herrmann, J.J.Haider, R.W.Fischer, Rhenium-Catalyzed Oxidation of Arenes - an Improved Synthesis of Vitamin K3, J. Mol. Catal. A: Chem. 138 (1999) 115]. Selectivity for MNH reaches 60% conversion MN 65%. Thus, the total yield of product amounted to only 39%.

Common disadvantages of all of the processes of obtaining MNH by oxidation of MN with the use of catalysts is the difficulty of obtaining and their high cost, difficulty of regeneration of heterogeneous catalysts and incomplete conversion of MN.

You know the MN oxidation by hydrogen peroxide in acetic acid without catalyst [US 6579994, SS 46/04, 12.12.02]. The authors received almost 100% selectivity and conversion. However, we used a sufficiently high temperature (100C) and reaction time was 3 hours.

In industry and MNH get mainly by stoichiometric oxidation of MN oxide chromium (VI) in sulfuric acid with a yield of 40-50% [L.F.Fieser, Convenient procedures for the preparation of antihemorrhagic compounds, J. Biol. Chem. 133 (1940) 391].

The closest to the technical nature of the claimed is a method for MNCH by oxidation of MN salts of hexavalent chromium in sulfuric acid [US 3751437, SS 49/66, 07.08.1973]. The reaction is carried out in batch and continuous modes. MN is dissolved in carbon tetrachloride, and then mixed with an aqueous solution of salt of chromium. The mixture is heated to 65-70C and maintained under stirring for 45 minutes Then add 76% sulfuric acid and incubated the mixture for another 90 min at the same temperature. Next, carbon tetrachloride with dissolved MNH decanted and distilled under vacuum. Conversion is 94%, the total yield is 57-61%. As the inert solvent is allowed to take acetic acid, chloroform, dichloroethane, benzene, etc. Oxidants are compounds of hexavalent chromium, such as sodium chromate, sodium bichromate, chromium oxide (VI), etc. as a mineral acid using sulfuric and hydrochloric acids. When the continuous mode of synthesis solutions MNH, bichromate and acid are served simultaneously in a tubular reactor at a certain speed. The way to get MNH is following the disadvantages. First, the use of expensive and toxic organic solvents, which you must then drive away. Second, the main characteristics of the process - the conversion of the parent compound and the yield of the target product is not high enough - 94% and 57-61%, respectively.

The objective of the invention is to develop a simpler method of obtaining MNH with high conversion, with a higher yield, as well as using waste products.

Tasked with securing MNH solved in the proposed method, the oxidation of MN chromiferous spent electrolyte content of hexavalent chromium 150-500 g/l in terms of CrO3in the form of a mixture with H2SO4or CH3COOH is added slowly to a pre-heated to 35-40C, MN, and then the temperature of the reaction mixture increased to 70-90C and incubated for 40-90 minutes

The technical result of the proposed method is to simplify the process, increase conversion and yield of the target product is reached only at observance of all process parameters.

Namely, in pre-heated to 35-40C MN under intensive stirring, slowly add the oxidizing mixture, while the temperature in the reactor is maintained at 40C. Only after adding all of the oxidizer temperature was raised to 70 to 90C. and the mixture is kept for 40-90 minutes Further to ablaut excess water, fallen MNH filtered off, washed with water chromium salts and dried. Oxidizing the mixture is prepared in advance by mixing chromium waste acid. The temperature of mixing of reagents at 35-40C is due on the one hand the melting point of MN, and on the other hand undesirable oxidation at high temperatures generated MNH with the formation of side products. After the introduction, the amount of oxidizing mixture, the temperature was raised to 70 to 90C for complete oxidation of MN as at a lower temperature not all MN has time to react. The optimal reaction time of 60 minutes At an earlier completion of the process, part of the MN remains unreacted at a later begins to significantly oxidize MNH to products.

The obtained product was analyzed by gas chromatography.

The claimed method of obtaining MNH illustrated by the following examples:

1. In thermostatted at 40C reactor equipped with a stirrer and reflux condenser, are placed 5 g of MN. After MN melts, it added slowly oxidizing mixture. Oxidizing the mixture represents a 100 ml aqueous waste electrolytic production containing hexavalent chromium concentration of 150 g/l in terms of CDF3mixed with 30 ml of sulfuric acid. After adding the oxidizing CME and, the reactor is heated to 70C and incubated for 60 minutes Then the mixture was added 50 ml of water, cooled to room temperature, precipitated MNH filtered and washed with water. Dried at 70C. the mass of the crude product is 4,36, the Basic substance of 93%. Conversion of 98%. Yield 67%. Next MNH purified by recrystallization in isooctane or any other non-polar solvent.

2. Everything is the same as in example 1, except that the oxidizing mixture is a 50 ml aqueous waste electrolytic production containing hexavalent chromium concentration of 300 g/l in terms of CrO3mixed with 17 ml of sulfuric acid. Weight of crude product is 4,68, the Basic substance of 88%. Conversion of 99%. Yield 68%.

3. Everything is the same as in example 1, except that the oxidizing mixture represents a 30 ml aqueous waste electrolytic production containing hexavalent chromium concentration of 500 g/l in terms of CrO3mixed with 10 ml of sulfuric acid. Weight of crude product was 5,14, the Basic substance of 80%. Conversion of 100%. Yield 68%.

4. Everything is the same as in example 2, only the mixture is heated to 80C and incubated for 60 min. Weight of crude product is 4,70, the Basic substance of 85%. Conversion of 100%. Yield 66%.

5. Everything is the same as in example 2, only the mixture is heated to 70C and incubated for 40 min. Weight of crude product is 4.05, the Main substance of 94%. onverse 95%. Yield 63%.

6. Everything is the same as in example 2, only the mixture is heated to 70C and incubated for 90 min. Weight of crude product is 4,78, the Main substance of 81%. Conversion of 100%. Yield 63%.

7. Everything is the same as in example 2, only 2-methylnaphthalene add to the rector of thermostatted at 35C. the mass of the crude product is 4,69, the Basic substance of 88%. Conversion of 99%. Yield 68%.

8. In thermostatted at 40C reactor equipped with a stirrer and reflux condenser, are placed 5 g of MN. After MN melted, slowly add the oxidizing mixture. Oxidizing the mixture represents a 100 ml aqueous waste electrolytic production containing hexavalent chromium concentration of 150 g/l in terms of CrO3mixed with 100 ml of acetic acid. After adding the oxidizing mixture, the reactor is heated to 90C and incubated for 60 minutes Then the mixture was added 200 ml of water, cooled to room temperature, precipitated MNH filtered and washed with water until disappearance of a greenish hue. Dried at 70C. the mass of the crude product is 3,79, the Basic substance of 99%. Conversion of 100%. Yield 62%. Next MNH purified by recrystallization in isooctane or any other non-polar solvent.

9. Just as in example 8, only oxidizing mixture consisted of 50 ml of water waste electrolytic production is TV, containing hexavalent chromium concentration of 300 g/l in terms of CrO3mixed with 50 ml of acetic acid. Upon completion of the reaction the mixture was added 100 ml of water, cooled to room temperature, precipitated MNH filtered and washed with water until disappearance of a greenish hue. Dried at 70C. the mass of the crude product is 3,85, the Basic substance of 99%. Conversion of 100%. Yield 63%.

10. Just as in example 8, only oxidizing the mixture represents a 30 ml aqueous waste electrolytic production containing hexavalent chromium concentration of 500 g/l in terms of CrO3mixed with 30 ml of acetic acid. Upon completion of the reaction the mixture was added 100 ml of water, cooled to room temperature, precipitated MNH filtered and washed with water until disappearance of a greenish hue. Dried at 70C. the mass of the crude product is 3.91, the Basic substance of 99%. Conversion of 100%. Yield 64%.

The aggregated results of the process according to examples 1-10 are shown in table.

Oxidation of 2-methylnaphthalene to 2-methyl-1,4-naphthoquinone chrome waste galvanic productions
ExampleThe concentration of chromium waste, g/l in terms of CrO3 SolventThe duration of reaction, mint, COutput MNH, mol.%Conversion of MN, mol.%The purity of the product, wt.%
1150H2O+H2SO46070679893
2300H2O+H2SO46070689988
3500H2O+H2SO460706810080
4300H2O+H2SO460806610085
5/td> 300H2O+H2SO44070639594
6300H2O+H2SO490706410081
7*300H2O+H2SO46070689988
8150CH3COOH60906210099
9300CH3COOH60906310099
10500 CH3COOH60906410099
* - 2-methylnaphthalene placed in the reactor thermostatted at 35C.

Thus, the proposed method for MNH allows to obtain the target product with a higher yield and purity. In addition, the proposed method for MNH is both a method of disposal of waste galvanic production, which currently either kill or reduced to trivalent chromium. Obtained in this process, the salt of trivalent chromium suitable for the production of leather tanning agent. Thus, the proposed technology is virtually waste-free and allows the use of waste containing hexavalent and trivalent chromium.

The method of obtaining 2-methyl-1,4-naphthoquinone by oxidation of 2-methylnaphthalene compounds hexavalent chromium in acidic medium by heating, characterized in that compounds of hexavalent chromium using chromium the spent electrolyte content of hexavalent chromium 150-500 g/l in terms of CrO3in the form of a mixture with sulfuric or acetic acid is added slowly to a pre-agreeme to 35-40C 2-methylnaphthalene, and then the temperature of the reaction mixture increased to 70-90C.



 

Same patents:

FIELD: organic chemistry, organic synthesis, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 2-methyl-1,4-naphthoquinone (menadione, vitamin K3) that is used broadly in medicinal practice and animal husbandry. Method for synthesis of 2-methyl-1,4-naphthoquinone involves oxidation of 2-methyl-1-naphthol with oxygen or oxygen-containing gas in medium of a low-polar or nonpolar organic solvent or in 2-methyl-1-naphthol melt at intensive stirring, under pressure 1 atm, not less, and temperature 20°C, not less. Method provides simplifying technology and preparing the end product of high purity and high yield.

EFFECT: improved preparing method.

4 cl, 1 tbl, 17 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing 1,4-naphthoquinone that is used in medicine in producing vitamin K and different industrial catalysts. Method is based on isolation of 1,4-naphthoquinone from waste in phthalic anhydride manufacturing wherein these waste are diluted with scrubber liquid and stirred. Mixture is heated up to the complete dissolving phthalic acid and distillation of 1,4-naphthoquinone is carried out at temperature 90-110°C with feeding live steam. Prepared vapor-like phase is cooled up to crystallization of 1,4-naphthoquinone followed by filtration of its aqueous solution and the following drying of the ready product by indirect heating. Method provides utilization of waste and preparing 1,4-naphthoquinone of the high purity degree.

EFFECT: improved preparing method.

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The invention relates to the production of alkyl substituted quinones by oxidation of alkylaromatic compounds by hydrogen peroxide, in the presence of porous amorphous titanium silicate catalyst - aerogel or xerogel, with a titanium content of not less than 0.2 wt.%

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The invention relates to organic synthesis, and in particular to an improved method for producing 2-methyl-1,4-naphthoquinone (menadione) of the formula (I) having the properties of vitamin K, obtained by oxidation of 4-R-2-methyl-1-Naftalan, where R = a) H, b) CH3

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining 2-ethyl-1,4-napthoquinone (menadione, vitamin K3), which is widely applied in medical practice and livestock breeding, especially in poultry breeding, as preparation for improvement of blood clotting. Method consists in oxidation of 2-methylnapthtaline with hexavalent chrome compounds in acid medium at heating. As compounds of hexavalent chrome applied is chrome-containing waste electrolyte with content of hexavalent chrome 150-500 g/l in terms of CrO3, which in form of mixture with sulfuric or acetous acid is slowly added to preliminarily heated to 35-40C 2-methylnaphtholine, and then temperature of reaction mass is increased to 70-90C.

EFFECT: obtaining target product with high conversion and higher output when using production wastes.

1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2-methyl-1,4-naphthoquinone (menadione, vitamin K3) which is widely used as a preparation for improving blood clotting. The method involves oxidation of 2-methylnaphthalene-containing material with hexavalent chromium compounds in an acidic medium. The 2-methylnaphthalene-containing material used is a methylnaphthalene fraction sampled in temperature interval 235-245C with distillation of stillage bottoms formed when producing naphthalene from the naphthalene fraction of coal tar.

EFFECT: invention enables to obtain an end product using a simple and highly efficient method with higher utilisation of starting material.

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EFFECT: method enables to obtain the end product with high output.

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FIELD: organic chemistry, organic synthesis, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 2-methyl-1,4-naphthoquinone (menadione, vitamin K3) that is used broadly in medicinal practice and animal husbandry. Method for synthesis of 2-methyl-1,4-naphthoquinone involves oxidation of 2-methyl-1-naphthol with oxygen or oxygen-containing gas in medium of a low-polar or nonpolar organic solvent or in 2-methyl-1-naphthol melt at intensive stirring, under pressure 1 atm, not less, and temperature 20°C, not less. Method provides simplifying technology and preparing the end product of high purity and high yield.

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FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining 2-ethyl-1,4-napthoquinone (menadione, vitamin K3), which is widely applied in medical practice and livestock breeding, especially in poultry breeding, as preparation for improvement of blood clotting. Method consists in oxidation of 2-methylnapthtaline with hexavalent chrome compounds in acid medium at heating. As compounds of hexavalent chrome applied is chrome-containing waste electrolyte with content of hexavalent chrome 150-500 g/l in terms of CrO3, which in form of mixture with sulfuric or acetous acid is slowly added to preliminarily heated to 35-40C 2-methylnaphtholine, and then temperature of reaction mass is increased to 70-90C.

EFFECT: obtaining target product with high conversion and higher output when using production wastes.

1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2-methyl-1,4-naphthoquinone (menadione, vitamin K3) which is widely used as a preparation for improving blood clotting. The method involves oxidation of 2-methylnaphthalene-containing material with hexavalent chromium compounds in an acidic medium. The 2-methylnaphthalene-containing material used is a methylnaphthalene fraction sampled in temperature interval 235-245C with distillation of stillage bottoms formed when producing naphthalene from the naphthalene fraction of coal tar.

EFFECT: invention enables to obtain an end product using a simple and highly efficient method with higher utilisation of starting material.

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FIELD: chemistry.

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FIELD: chemistry.

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EFFECT: method enables to obtain the end product with high output using a simple and safe technique.

2 ex

FIELD: chemistry.

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EFFECT: method enables to obtain the end product with high output.

9 ex

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