The method of obtaining substituted phenol

 

(57) Abstract:

Use: in the production of substituted phenols. The inventive product f - crystals: (R,,)WITH IT. where (F bfly-H provided that. to say the least. R or R-H or C-C zmywarki, Arip. aralkyl, amino group, halogen or nitrogroup reaction Conditions: synthesis are carboxypropanoyl with subsequent hydrolysis in the liquid phase of the corresponding carboxylic acid in the presence of dissolved copper-containing catalyst, forming arylcarboxylic copper. When I downloaded the catalyst oxidizes oxygen-containing gas at 120-190° C, and then subjected to reaction with arylcarbamoyl acid in an oxygen-free environment in the presence of water collected in 40 - to 200-fold molar excess relative to the amount formed of alperbellikli. when 225-270° C and a pressure of 0.1 to 25 MPa Obtained substituted phenol is separated by distillation, and the catalyst is returned to the reaction zone for reuse. 2 t ABA

 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing hydroxyaromatic compounds by oxidation of aromatic compounds with nitrous oxide in gaseous phase in the presence of zeolites. Method is realized by interaction of aromatic compounds of the formula (I): Ar-Rn wherein Ar means benzene or naphthalene; R means bromine, chlorine, fluorine atom, -NO2, -CN, -NH2, hydroxy-group, alkyl with 1-6 carbon atoms or phenyl; n = 0, 1 or 2 with nitrous oxide in gaseous phase in the presence of zeolites taken among the following order: pentasil, ferrierite and zeolite-β. Zeolite crystallites size is less 100 nm that is calcined before using at temperature from 500°C to 1350°C for 0.5-18 h. Before the calcination process zeolite is modified preferably by precipitation of silane or borane. Method provides realization of the process for a single step with high yield of the end compound and minimal formation of by-side substances.

EFFECT: improved preparing method.

11 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: at first stage by continuous method phenol is obtained by direct benzol oxidation with hydrogen peroxide with ratio of H2O2/benzol from 10 to 70% mol., in three-phase reaction system, which includes first liquid phase, consisting of benzol and organic solvent, second liquid phase, consisting of water, and solid phase, consisting of activated catalyst, which contains titanium silicate TS-1. At second stage phenol and benzol which has not reacted are separated from reaction mixture by fraction distillation. At third stage solvent and by-products, containing dioxybenzols, are separated from mixture, supplied from tail fraction of second stage distillation, by extraction with base obtaining water solution of dioxybenzols. At fourth stage obtained water solution of dioxybenzols is converted into phenol by hydrodeoxygenation with hydrogen in conditions of continuous operation at temperature from 250 to 500°C, pressure 0.1-10 MPa and in presence of catalyst containing element of group VIB or their mixture or element of group VIII of periodic system or their mixture and promoter. At fifth stage obtained by re-cycle at previous stage phenol is supplied to distillation stage.

EFFECT: increase of degree of benzol conversion and selectivity on phenol, elimination of diphenol formation and reduction of solvents quantity.

22 cl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: method for producing a hydroxylation catalyst for aromatic compounds with nitrogen oxide, which is an iron-containing zeolite of the MFI structure and/or MEL with a binder, modified with the ruthenium compounds in the amount of 0.01-5.0 wt % based on the metal, the soluble ruthenium compound is introduced in the step of forming the zeolite with the binder, or after moulding and calcining, or after moulding, calcining and thermocouple processing. The catalyst is regenerated at the temperature of 450-475°C in an inert gas medium containing 1 to 2 wt % of oxygen.

EFFECT: maximum activity and selectivity of the catalyst.

7 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 4-tert-butyl pyrocatechol, which is widely used as an inhibitor of the polymerization of diene hydrocarbons, stabilizers of unsaturated aldehydes, polymeric materials, ethylcellulose artificial resins, antioxidants of oils, waxes and animal fats, insecticidal compounds, as well as in various fields of experimental biology, as well as to the catalyst used in this method. The method consists in the selective oxidation of 4-tert-butylphenol with aqueous solutions of H2O2 in the presence of a titanosilicate catalyst. Herewith Ti is used as a catalyst in an amount of 1.0 wt % deposited on the mesoporous carrier SiO2 produced by impregnating the carrier with a benzene solution of Ti(OC2H5)4, followed by drying in air at room temperature, treating with aqueous ammonia, drying at 120°C/4 hours and calcining at 550°C/4 hours, and the reaction is carried out in the presence of 2-10% (per reaction mass) of the catalyst in acetonitrile with a starting concentration of 4-tert-butylphenol 2.0 mol/l at a molar ratio of 4-tert-butylphenol: H2O2=1÷2:1 and a temperature of 30-50°C.

EFFECT: improved method.

2 cl, 1 tbl, 9 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of glucopyranosyloxybenzylbenzene represented by the formula (I): wherein R1 represents hydrogen atom or hydroxy(lower)alkyl; R2 represents lower alkyl group, lower alkoxy-group and lower alkylthio-group being each group is substituted optionally with hydroxy- or (lower)alkoxy-group, or to its pharmaceutically acceptable salts. Also, invention relates to pharmaceutical composition eliciting hypoglycemic activity and to a method for treatment and prophylaxis of hyperglycemia-associated diseases, such as diabetes mellitus, obesity and others, and to their intermediate compounds. Invention provides preparing new derivatives of glucopyranosyloxybenzylbenzene that elicit the excellent inhibitory activity with respect to human SGLT2.

EFFECT: valuable medicinal properties of compounds.

13 cl, 2 tbl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of phenol via acid catalytic decomposition of cumene hydroperoxide followed by isolation of phenol from decomposition products and purification of phenol to remove trace impurities including acetol. Purification of phenol is accomplished through hetero-azeotropic rectification with water. Acetol is isolated as a part of liquid-phase side stream from semiblind plate located within exhausting section of hetero-azeotropic rectification column. Side stream is supplemented by cumene and used to supply stripping column, from which fraction of acetol/cumene azeotropic mixture is taken as distillate and residue is returned under semiblind plate of hetero-azeotropic rectification column to be further exhausted. From the bottom of the latter, crude phenol is withdrawn and passed to final purification from the rest of reactive trace impurities. Acetol/cumene azeotropic mixture is subjected to heat treatment at 310-350°C, which may be performed in mixtures with high-boiling production waste or in mixtures with bottom product of rectification column for thermal degradation of high-boiling synthesis by-products, which bottom product is recycled via tubular furnace. Above-mentioned semiblind plate, from which side stream is tapped, is disposed in column zone, wherein content of water is minimal and below which contact devices are positioned with efficiency at least 7.5 theoretical plates. Side stream with cumene added to it is passed to the vat of stripping column with efficiency at least 15 theoretical plates.

EFFECT: minimized content of acetol in purified phenol and reduced power consumption.

5 cl, 3 dwg, 6 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to joint phenol-acetone production via selective decomposition of cumene hydroperoxide. Process is conducted in several in series connected reactors constructed in the form of shell-and-tube heat-exchangers, wherein part of decomposition product is recycled into reaction zone and mixed with feed stream to be decomposed, weight ratio of recycled stream to feed stream being less than 10. Reactors with tubular hydrodynamic characteristic have volumetric heat-exchange surface equal to or larger than 500 m2/m3. Preferably, residual concentration of cumene hydroperoxide is 0.1-0.3 wt % and its residence time in decomposition zone ranges from 0.5 to 10 min.

EFFECT: increased selectivity of decomposition at lesser recycle apparatus volume and reduced investment expenses.

11 cl, 1 dwg, 9 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to manufacturing phenol by cumene method, in particular, to a step for treatment of final product and preparing phenol of high purity degree. Method for treatment of crude phenol is carried out for two steps. At the first step method involves oxidation of acetol, aldehydes and α-methylstyrene with air oxygen in phenol medium by using a heterogeneous catalyst comprising metals with transient valence. At the second step method involves condensation of oxidation products and non-oxidized products by using a heterogeneous acid catalyst. Separation of compounds in the process of phenol treatment is carried out on the final step of isolation of the commercial product by distillation method. At the first stage metal compounds of by-side subgroups 1 and 6 and metals of 8 group of Periodic system on neutral or acid carrier are used as a catalyst preferably. At the second step alumosilicate contacts based on zeolites of type "X" or "Y", or other zeolites comprising or not comprising promoting and modifying additives are used as a catalyst. Invention provides the high degree of purification of phenol from impurities and the improvement of economy indices of the process.

EFFECT: improved method for phenol treatment.

12 cl, 5 ex

FIELD: chemical industry; methods of production of phenol and acetone.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the industrial process of production of phenol and acetone by the cumene method. The method is realized by decomposition of the technological cumene hydroperoxide in the in series connected reactors in two stages with formation on the first stage of the dicumylperoxide at the temperature of 40-65°С at presence as the catalytic agent of 0.003-0.015 mass % of the sulfuric acid with its subsequent decomposition on the second stage in the reaction medium at the temperature of 90-140°С. The process is conducted at the excess of phenol in the reaction mixture at the molar ratio of phenol : acetone exceeding 1, preferentially - from 1.01 up to 5. Excess of phenol is formed either by distillation (blowing) of acetone or addition of phenol in the reaction medium. The technical result of the invention is reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

EFFECT: the invention ensures reduction of formation of hydroxyacetone, which one worsens the quality of the commercial phenol.

5 cl, 4 ex, 8 tbl

FIELD: industrial organic synthesis.

SUBSTANCE: isopropyl alcohol production process comprises hydrogenation of starting acetone including from 0.01 to 10000 ppm benzene in presence of hydrogen and catalyst to give isopropyl alcohol and benzene hydrogenation products, acetone and benzene contained in feedstock being hydrogenated simultaneously. In its second embodiment, isopropyl alcohol production process comprises product separation stage. Process of producing phenol and isopropyl alcohol containing benzene hydrogenation products comprises stages: alkylation of benzene with isopropyl alcohol and/or propylene to form cumene, oxidation of resulting cumene into cumene hydroperoxide, acid cleavage of cumene hydroperoxide to produce phenol and acetone including from 0.01 to 10000 ppm benzene, preferably concentration of produced benzene-polluted acetone, and catalytic hydrogenation of benzene-polluted acetone into isopropyl alcohol containing benzene hydrogenation products, hydrogenation of benzene and acetone proceeding simultaneously.

EFFECT: enhanced process efficiency.

3 cl, 1 dwg, 1 tbl

FIELD: chemical industry; methods of extraction of phenol and biphenols from the homogeneous reactionary mixtures.

SUBSTANCE: the invention is pertaining to the method of extraction of phenol and biphenols from the homogeneous reactionary mixtures of the direct oxidation of benzene by hydrogen peroxide. The method includes delivery of the reactionary mixture containing benzene, water, phenol, the sulfolane and the reaction by-products (biphenols) in еру distillation plant consisting of two or more columns for production of one or more products basically consisting of the azeotropic mixture of benzene with water and phenol, and also the product consisting of sulfolane, phenol and the reaction by-products. The stream including sulfolane is mixed with the water solution of the base and benzene for formation of the salts of the phenols and the subsequent stratification of the mixture, extraction by benzene and separation in the flow column containing benzene and sulfolane, which is returned in the reactor. From the same column separate the stream including sodium phenolates in the water solution, which is treated with the sulfuric acid for extraction of the phenols from their salts. At the stage of the extraction separate the extracting solvent, after distillation of which in the tailings bottom product receive the biphenols water solution. The separated organic solvent recirculates in the system. The technical result of the invention is improvement of the process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

EFFECT: the invention ensures the improved process of separation of phenols and biphenols from the complex azeotropic mixtures containing sulfolane.

9 cl, 1 ex, 1 dwg, 1 tbl

FIELD: chemical industry; methods of production of the phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone.

SUBSTANCE: the invention is pertaining to production of phenols by the catalytic decomposition of the cumene hydroperoxide into phenol and acetone. The method provides for oxidization of the cumene into the cumene hydroperoxide, catalyzed by the acid decomposition of the cumene hydroperoxide, neutralization of the produced product of the decomposition, maintaining the product in the homogeneous phase before neutralization, which is conducted by means of the aqueous base. The phenol is separated by fractionation of the neutralized product. The aqueous base represents the water solution of the sodium hydroxide or phenoxide. In particular use the regenerated phenoxide, at least, on one phase of the treatment at production of the phenol. It is preferential to add the sodium hydroxide water solution to the reaction product in such a concentration and such amount, that to receive the concentration of sodium phenolate in the homogeneous phase from 0.2 up to 2.5 mass %. The temperature of the homogeneous phase after the add-on of the aqueous base is set within the range of 20°С-150°С, the preferable temperature is within the range of 60°С-120°С. It is preferential, that the reaction product is saturated with the oxygen-containing gas. The technical result of the invention is the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.

EFFECT: the invention ensures the decreased quantity of the undesirable impurities in the products of the acid decomposition of the cumene hydroperoxide.

13 cl, 4 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for purifying phenolic flow prepared after distillation of raw acetone in separating decomposition products of cumene hydroperoxide from hydroxyacetone by rectification method. For removal of hydroxyacetone from phenolic flow methods of azeotropic-extractive rectification is used with using a combined separating agent wherein hydrocarbon (cumene and/or α-methylstyrene) is used as one components, and water is used as another component. Method involves feeding a separating agent in common with feeding a column, maintaining the mass ratio of hydrocarbon and water that equal or above the mass ratio of concentrations of hydrocarbon and water in the corresponding azeotropic mixtures, removing hydroxyacetone from column with distillate aqueous flow and feeding organic phase to phlegm wherein this organic phase is depleted with hydroxyacetone. Use of this method provides enhancing selectivity and complete distillation of hydroxyacetone.

EFFECT: improved purifying method.

17 cl, 2 dwg, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining phenol and acetone by acid-catalysable decomposition of hydro-peroxide of cumene in the environment of the reaction products at elevated temperatures in one stage. In this case the process is carried out in the presence of a catalyst, prepared immediately before its introduction into the reactor for the decomposition of hydro-peroxide of cumene by mixing sulfuric acid with phenol at the ratio of from 2:1 till 1:1000 and the waiting time from mixing till putting into the reactor for the decomposition of hydro-peroxide of cumene from 1 to 600 minutes at a temperature from 20 to 80°C. As a rule, sulfuric acid has a concentration of higher than 75% or oleum is used.

EFFECT: it makes it possible to decrease the output of the by-product hydroxyacetone, improves the quality of market-grade phenol and decreases the consumption of sulfuric acid.

2 cl, 4 tbl, 4 ex

FIELD: industrial organic synthesis.

SUBSTANCE: purification of industrial-grade resorcinol mainly comprises removal of phenol by way of disintegrating product at 40-60°C in inert gas or air flow to particle size 0.01-0.1 mm. Depending on pollution and content of phenol in starting resorcinol, disintegration is preceded by extraction of resorcinol with alcohol or ketone, or ether, or water, after which resorcinol is dried in inert gas flow at 20-40°C. Purified product has melting point 110°C and is characterized by phenol level not exceeding 0.001 wt %.

EFFECT: improved quality of product and simplified purification process.

2 cl, 2 ex

FIELD: analytical methods.

SUBSTANCE: invention is directed to controlling treated waste waters from varnish-and-paint industry enterprises and discloses a method of separately determining resorcinol and 2,4-dinitroresorcinol involving potentiometric titration in dimethylformamide medium, determination being carried out in aqueous sample preliminarily acidified to pH 2-3 and treated with acetone in presence of ammonium sulfate as salting-out agent in amount 36.5-40.0% of the weight of sample. Organic layer containing resorcinol and 2,4-dinitroresorcinol is then separated, diluted with dimethylformamide at volume ratio 1:5, and titrated with solution of potassium hydroxide in isopropyl alcohol. Content of each of resorcinols is calculated from differential titration curves in according to formula: C = Co100/R wherein C and Co are concentrations of resorcinols in initial aqueous sample and in extract, respectively, mg/dm3, and R degree of recovery of resorcinols in acetone/water-salt solution, %.

EFFECT: enabled selective determination of resorcinol and 2,4-dinitroresorcinol, reduced detection limits (extraction concentration operation), and expanded application area.

2 tbl, 12 ex

FIELD: analytical chemistry of organic compounds; in particular quality controlling of alcohol products.

SUBSTANCE: claimed method includes catechol extraction from ground oak wood with organic solvent aqueous solution followed by determination of content thereof, wherein as organic solvent ethanol aqueous solution is used in ethanol/water ratio of 50:50. Then catechols are concentrated into organic phase at pH 2.0-3.0; ammonium sulfate is added in amount of 18-20 % based of probe mass and catechols are determined by extract conductance-measuring titration. Catechol content in aqueous alcohol solution as calculated to quercetine is determined according formula wherein C is catechol concentration in solution, g/dm3; C(PB(NO3)2) is molar concentration of titrant equivalent, g/dm3; V(PB(NO3)2) is titrant volume required for catechol titration, cm3; Mk - molar mass of quercetine, g/mol; Ve - extract volume, cm3; r is equilibrium volume ratio of aqueous and organic phases; R is catechol recovery degree in ethanol/aqueous-salt solution, % (96).

EFFECT: simplified and inexpensive method with increased selectivity, and enhanced applications.

9 ex, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: process includes resorcinol extraction with organic solvent tributyl phosphate (TBPh). The well-milled hard foamed polyurethane (FPU) will be modified at that with tributyl phosphate in the mass ratio FPU:TBPh = 1:(2.0-2.5), the extraction will be performed prior to establishing the interphase balance with subsequent isolation of organic phase from the water phase.

EFFECT: process enables one to enhance the concentrating coefficient and reduce expenditure of the organic solvent tributyl phosphate.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: flow of water solution of dioxybenzole with concentration from 5 to 60 wt % with volume rate, expressed in kg of dioxybenzole/hour/kg of catalyst 0.1 - 10 hours-1, and hydrogen flow are supplied to adiabatic reactor with immobile layer of catalyst. Reaction of hydrodeoxygenation in vapour phase working in continuous regime in presence of catalyst is performed. Flow of dioxybenzole water solution and hydrogen flow are supplied in such amount that ratio between total quantity of hydrogen and dioxubenzole moles was within range from 2:1 to 50:1. Reaction is carried out at temperature within range from 250 to 500°C and pressure 0.1-10 MPa. Used catalyst represents catalyst on carrier, containing element of group VIB, or their mixture, or element of group VIII of periodic system, or their mixture and promoter.

EFFECT: invention allows to increase decree of dioxybenzole conversion, selectivity in relation to phenol and process productivity.

21 cl, 27 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of organic compounds and a method of concentrating resorcinol from aqueous solutions, involving extraction-sorption concentration of resorcinol using a sorbent in form of elastic foamed polyurethane modified with a solution of tributylphosphate in hexane in volume ratio of tributylphophate: hexane equal to 1:(0.5-1) and weight ratio of elastic foamed polyurethane: tributylphosphate equal to 1:(0.5-0.75).

EFFECT: high coefficient of extraction-sorption concentration, increase in degree of extraction to 98,6% and low consumption of tributylphosphate.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying crude hydroquinone HQ0, essentially containing hydroquinone and small amounts of impurities, containing both: (i) impurities having a lower evaporation temperature than that of hydroquinone, referred to as light impurities, including resorcinol; and (ii) impurities having a higher evaporation temperature than that of hydroquinone, referred to as heavy impurities, including pyrogallol. Said method is characterised by that is includes the following steps: (A) distillation in the top part of the column, in which the crude hydroquinone HQ0 is injected into a distillation column, having reflux ratio from 300 to 2000, and where the resorcinol is removed in the top part of the column, optionally in conjunction with all or part of the other light impurities, whereby a crude mixture M, containing hydroquinone and heavy impurities, is recovered in the bottom part of the column; and (B) distillation in the bottom part of the column, in which the crude mixture M obtained in step (A) is injected into the distillation column and where pyrogallol is removed in the bottom part of the column, optionally in conjunction with all or part of the other heavy impurities, whereby hydroquinone in purified form (HQ), having impurity content less than 4000 ppm, is recovered in the top part of the column.

EFFECT: invention is a cost-effective method for purifying hydroquinone.

18 cl, 1 ex, 2 dwg

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