The method of obtaining carbonyl compounds |
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IPC classes for russian patent The method of obtaining carbonyl compounds (RU 2227133):
        
 The way to obtain (6r,10r)-6,10,14-trimethylpentene-2-it (fiona) / 2197465
The invention relates to the field of synthesis of terpenoid ketones, and in particular to an improved method of obtaining Fiona, which can be used in the synthesis of vitamins E and K
 The method of obtaining oxygen-containing organic compounds - mixtures of ketones and unsaturated alcohols and aldehydes may / 2174113
The invention relates to the field of production of oxygen-containing organic compounds, ketones, unsaturated alcohols and possibly aldehydes by isomerization WITH5-epoxides in the presence of a homogeneous catalyst
The way to obtain 1-phenyl-1-(alkyl)phenylacetone / 2151138
The invention relates to a method for producing 1-phenyl-1-(alkyl)phenylacetone, which is an intermediate for obtaining rodenticide preparations of 2-(
 -phenyl--(alkyl)phenylacetyl)indandione-1,3, in particular ethylbenzene(alkyl R = C2H5and izinduna (alkyl R = ISO-C3H7) used for the control of rodents
 The method of obtaining lower ketones / 2123994
The invention relates to the production of lower ketones liquid-phase dehydrogenation of secondary alcohols in the presence of a fixed catalyst - Nickel metal or activated hydrogen Nickel metal or Nickel on the carrier in the environment paraffins C12-C20that process is used as solvent, the drying means, the environment for the activation of the catalyst and carrier
 The method of obtaining pinacoline / 2110509
 The method of obtaining pinacoline / 2107680
 A method of obtaining a lower saturated aliphatic or cyclic ketones and acid catalytic system for their production / 2060987
The invention relates to a method for producing ketones, in particular to a method for producing ketones using reaction paired diolefines and water, and thus obtained ketones
Synthesis and purification of 3,3-dimethylbutyramide through the oxidation of 1-chloro-3,3-dimethylbutane dimethylsulfoxide (options) / 2217410
The invention relates to methods of obtaining and purification of 3,3-dimethylbutyramide
 A method of producing aldehydes / 2212396
The invention relates to a method for producing an aldehyde intermediate of organic synthesis
 The method of obtaining saturated monoallelic / 2205174
The invention relates to a method for saturated monoallelic - intermediate products of organic synthesis
The method of obtaining oxygen-containing organic compounds - mixtures of ketones and unsaturated alcohols and aldehydes may / 2174113
The invention relates to the field of production of oxygen-containing organic compounds, ketones, unsaturated alcohols and possibly aldehydes by isomerization WITH5-epoxides in the presence of a homogeneous catalyst
 The method of obtaining the oxidized products / 2140897
The invention relates to processes for the oxidized products, namely the processes of obtaining the oxidized products enriched in olefins feedstock
The allocation method n-butyric aldehyde product of propylene hydroformylation / 2130917
The invention relates to chemical technology, namely the allocation method n-butyric aldehyde (IA) in the process of oxosynthesis
 The method of producing corrosion inhibitor / 2086531
The invention relates to oxygen-containing compounds, in particular to the processing of still residue of butyl alcohols production method oxosynthesis, more specifically to an improved method of processing waste products of alcohols and aldehydes by the method of propylene hydroformylation
 The method of obtaining isovalerianic aldehyde / 2074851
The invention relates to petrochemistry, namely the method of production of isovalerianic aldehyde, which is used in the pharmaceutical industry (drugs cardiology appointment)
A method of producing aldehydes / 2212396
The invention relates to a method for producing an aldehyde intermediate of organic synthesis
 Solid acid catalyst, process for its production and its use / 2190465
The invention relates to a solid molded the catalysts are easily separated from the reactants and re-used in the reactions of alkylation, esterification and isomerization
 Method for production of carbonyl compounds / 2270185
Claimed method includes reaction of nitrous oxide with alkenes in presence of inert gas as diluent. Reaction is carried out in gas phase at 401-700°C and under pressure of 2-300 atm. Target compounds represent value intermediates for precise and base organic synthesis.
 Method for preparing xanthophyll / 2284992
Invention relates to the improved method for preparing xanthophylls, in particular, to a method for preparing mono- or polyoxidized xanthophylls. Method involves oxidation of carotinoid in a lower oxidation state as compared with xanthophylls to be prepared from hydrogen peroxide aqueous solution and organic solvent wherein indicated solvent represents a water-insoluble solvent. Indicated reaction is carried out in the presence of iodine-containing compound chosen from the group including iodine, iodine halide derivative and metal iodide. Method allows avoiding using danger and expensive substances and formation of large amounts of salts. The proposed invention is used mainly for oxidation of beta-carotene to form canthaxanthine and oxidation of lutein and zeaxanthine wherein the end substances represent important agents used in preparing food compositions and supplements in animal fodder.
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(57) Abstract: The invention relates to a method for producing carbonyl compounds with the number of atoms2-C40. The method consists in the reaction of liquid-phase oxidation of aliphatic alkenes WITH2-C40formula (I) where R1, R2, R3, R4radicals that can be represented by atoms of hydrogen, alkyl, alkenylamine or aryl radicals, including those containing functional groups, in addition to radicals, which include in their composition nonaromatic carbocycle, having in its composition a double bond C=C, carbonyl compounds, nitrogen oxide in the presence of an inert gas diluent, at a temperature of 100-3500And pressure of nitrous oxide 1.5 to 100 ATM. The process provides a high selectivity for the target products, the explosion of work and is promising for industrial applications. 4 C.p. f-crystals, 3 tables. The invention relates to a method for producing carbonyl compounds with the number of atoms2-C40more specifically the way they are received by the liquid-phase oxidation of aliphatic alkenes WITH2-C40nitrous oxide (N2O). Carbonyl. the no is also widely used as solvents. Carbonyl compounds receive mainly by oxosynthesis, the oxidation of hydrocarbons or by the dehydrogenation of alcohols. However, these methods are not efficient enough, so a search for better methods of their synthesis [R. Fisher et al., U. S. Pat. No. 6303828, 2001; C. Kohlpainter, R. Fisher, B. Kornils, Appl. Catal. A:, 2001, vol.221, N. 1-2, p.219-225; T. Yokoyama, N. Yamagata, ibid., p.227-239]. In the patent GB Pat. 649680 (1951) claimed method oxidation of olefins to carbonyl compounds nitrous oxide. According to this method, in particular, may receive carbonyl compounds by oxidation of aliphatic alkenes. The main disadvantage of this method is the possibility of formation during the process of flammable mixtures of alkene - nitrous oxide”. To eliminate the risk, the authors of patent offer to additionally enter into the reaction mixture of saturated hydrocarbons. However, as shown by more recent studies, a mixture of saturated hydrocarbons with N2O almost as explosive as a mixture of olefins. Thus, the maximum concentrations of propylene in N2O is 1.8-26.8 per cent, and the maximum concentrations of propane 2,1-24,8% [G. Panetier, A. Sicard, V Symposium on Combustion, 620 (1955); B. B. Brandt, L. A. Moreaction ability, cannot serve as a means to avoid the explosion. This patent discloses a method of producing aldehydes and ketones by oxidation of aliphatic alkenes with nitrous oxide, N2Oh, in the presence of inert gas, which does not have these disadvantages. According to this method, the reaction is carried out in the presence of inert gas under the conditions when the alkene is present in the form of a liquid phase in which the oxidation reaction proceeds with high selectivity. Excessive increase in the temperature and/or pressure N2O is undesirable because it may result in a loss of selectivity due to the contribution of gas-phase oxidation. The composition oxidize alkenes can be expressed by the formula (I) where Riradicals that can be represented by atoms of hydrogen, alkyl, alkenylamine, aryl or other organic radicals, including those containing functional groups, in addition to radicals which comprise non-aromatic Carbo - or heterocycles having carbon atoms with a double bond. Intrinsically safe working conditions for the proposed method are provided by adding to the reaction mixture an inert gas not entering't play flue gases of the reaction or recirculating gases. At different stages of the process, depending on the ratio of alkene : nitrous oxide, the proportion of inert gas required to provide proof of work can be different and be created by a separate feeder. From the point of view of simplicity and maximum process safety it is advisable to have this dilution nitrous oxide inertnet gas, to the reaction mixture was explosive in any content alkene. This condition is satisfied if the content of N2O in a mixture with inertnet gas is not more than 25%. Apply this mixture eliminates the occurrence of hazardous situations at all stages of the process. To reduce the explosion hazard in the reaction mixture can be added flame retardants, such as trifloromethyl, diperchlorate, dibromotetrafluoroethane etc. In accordance with this invention the oxidation of aliphatic alkenes to aldehydes and ketones nitrogen oxide in the presence of inert gas can be carried out in a wide range of conditions both in static and flow-through reactor, which may be made of steel, titanium, glass or other suitable material. This can be used all known technological PR is injected alkene (with solvent or without solvent) in such amount, so that when heated to the reaction temperature, he was present as a liquid phase. The oxygen in the reactor as opposed to a mixture of nitrous oxide with inert gas and increase the pressure to a predetermined value. The amount of nitrous oxide selected so that its pressure at the reaction temperature was 1.5-100 ATM. The concentration of inert gas in the mixture with nitrous oxide selected so that it does not exceed 99%. Then the reactor is heated to the reaction temperature in the region of 100-350°C. the reaction Time is selected depending on the conditions of its implementation, as well as the requirements process, and may vary from several minutes to several tens hours. The proposed process can be carried out without solvents. However, it is possible to conduct the process and with the use of solvents which can be selected from a wide range of substances commonly used in the practice of organic synthesis. Reaction with high speed proceeds without a catalyst, although it may also be carried out in the presence of a catalyst. In some cases, to suppress side to alkene is advisable to add inhibitors of dimerization and polymerization. The proposed method polucheniya as in pure form, and with admixtures of various gases, will have no adverse impact on rates of reaction. The original alkene may also contain various organic impurities, especially if they do not contain double bonds C=C. The essence of the invention is illustrated by the following examples. Examples 1-2 Example 1. This example is comparative. In a reactor with a volume of 100 cm3made of stainless steel and equipped with a mixer (firm Parr), pour 25 cm31-octene (Aldrich, 99%). The reactor is rinsed with nitrogen and then brought her pressure up to 10 ATM. The reactor was sealed, heated to 220C and kept at this temperature for 10 hours. The pressure of nitrous oxide when the reaction temperature is 30 ATM. After the reaction, the reactor is cooled to room temperature and analyze the final composition of the gas and liquid phases by the methods of gas chromatography and chromatomasspectrometry. Sometimes for more precise identification of the reaction products using the NMR method. The conversion of 1-octene and the selectivity of the reaction products is calculated by the following equations: where Cithe concentration of the i-th reaction product, - initial Conca and final concentrations of alkene In the reaction, the conversion of 1-octene is 16%. The reaction leads to the formation of the following oxygen-containing products: 2-octanone (44%), octanal (33%), heptanal (23%). The total selectivity for these products is 57% (table.1). Example 2 same as example 1 with the difference that instead of pure nitrous oxide in the reactor serves its mixture with an inert gas - nitrogen, in which the concentration of N2About 20% (table.1). The initial pressure of the mixture in the reactor, R0set of 90 ATM. The pressure of nitrous oxide when the reaction temperature is 30 ATM. In the reaction, the conversion of 1-octene was 16.5%. In the reaction products detected the following oxygen-containing compounds: 2-octanone (46%), octanal (32%), heptanal (22%), which are formed with a total selectivity of 60% (table.1). This example shows that the reaction of the liquid-phase oxidation of aliphatic alkenes to carbonyl compounds proceeds with retention of conversion and selectivity when used as an oxidizer mixtures of nitrous oxide with inert gas. Examples 3-5 Examples 3-5 show the possibility of carrying out the reaction using mixtures of nitrous oxide with inert gasesous a mixture of nitrous oxide from nitrogen, in which the concentration of N2O is 70%, and the initial pressure in the reactor was set to 80 ATM. The experience carried out at 100 C for 60 hours. Pressure N2O when the reaction temperature is 100 ATM. Example 4 same as example 2, with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 1%, nitrogen - 99%. The initial pressure of the mixture in the reactor was set to 100 ATM. The experience carried out at 250°C for 20 hours. Pressure N2O when the reaction temperature is 1.5 ATM. Example 5 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O 95% nitrogen - 5%. The initial pressure of the mixture in the reactor set 28 ATM. The experience carried out at 200°C for 12 hours. Pressure N2O when the reaction temperature is 70 ATM. Examples 6-11 Examples 6-11 show the possibility of selective oxidation of 2-pentene in 2 - and 3-pentanone using mixtures of nitrous oxide with inert gases of different composition, including the use of solvents. In table. 3 shows the conversion of 2-pentene under different reaction conditions, as well as the total behold the example 6 describes the oxidation of 2-pentene. The experience carried out analogously to example 2 with the difference that as the starting alkene take 2-penten. To achieve this, prior experience in reactor pour 25 ml of 2-pentene. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 50%, and the initial pressure is set to 30 ATM. The experience carried out at 198°C for 12 hours. Pressure N2About when the reaction temperature is 28 ATM. Example 7 same as example 6 with the difference that experience lead at 190°C for 15 hours, using as solvent mesitylene. To achieve this, prior experience in reactor pour 10 ml of 2-pentene and 50 ml of mesitylene. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O 70%. The initial pressure of the mixture set 18 ATM. Pressure N2O when the reaction temperature is 34 ATM. Example 8 is similar to example 7 with the difference that the solvent used toluene, and the experience is conducted at 200°C for 5 hours. Pressure N2O when the reaction temperature is 35 ATM. Example 9 same as example 7 with the difference that the concentration of nitrous oxide in a mixture with nitrogen is 25%, and the initial pressure of the mixture in the reactor set 80 at which the reaction temperature is 34 ATM. Example 10 same as example 7 with the difference that as the inert gas instead of nitrogen gas used argon, in which the concentration of nitrous oxide 50%, and the initial pressure of the mixture in the reactor was set to 30 ATM. As the solvent used isobutyl alcohol. The experience carried out at 190°C for 15 hours. Pressure N2About when the reaction temperature is 34 ATM. Example 11 same as example 10 with the difference that instead of argon using carbon dioxide. Examples 12-13 Examples 12-13 (PL.3) show the possibility of conducting the process in the presence of a catalyst. Example 12 same as example 7 with the difference that the reaction is carried out in the presence of catalyst (0.2 g Fe2O3/SIO, SIS2(2.8 wt.% Fe2ABOUT3). The catalyst is prepared by impregnation of SIO, SIS2a solution of FeCl3, dried at 110°C and calcined in air at 500°C for 2 hours. Example 13 same as example 8 with the difference that the reaction is carried out in the presence of catalyst (0.3 g Ag/SiO2(1 wt.% Ag). The catalyst is prepared by impregnation of SIO, SIS2a solution of AgNO3, dried at 110°C and calcined in air at 500°C for 2 hours. Example 14 This is an example of aflaai such load all 2-penten under the reaction conditions is in the gas phase. Experience the conversion of 2-pentene was about 0.5%. This shows that under these conditions the reaction in the gas phase is hardly taking place. Examples 15-25 These examples demonstrate the possibility of oxidation with nitrous oxide in a mixture with an inert gas, various aliphatic alkenes and their derivatives, including as radicals at C=C bond, the hydrogen atom, alkyl, alkeline or aryl radicals and functional groups. Example 15 describes the oxidation of propylene using as solvent mesitylene. In the reactor at room temperature, pour 50 ml of mesitylene and serves propylene to a pressure of 7 ATM. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O 70%. The mixture was fed to the reactor was set total pressure of 25 ATM. The experience carried out at 200°C for 12 hours. Pressure N2O when the reaction temperature is 36 ATM. The conversion of propylene is 10%. Oxygen-containing products of the reaction are acetone, propionic aldehyde and acetaldehyde in the approximate molar ratio of 1: 0,4:0,15. Example 16 describes the oxidation of styrene. In the reactor at room temperature, pour 5 ml stir the ATEM serves a mixture of nitrous oxide from nitrogen, in which the concentration of N2O 95%. The initial pressure of the mixture in the reactor was set to 12 ATM. The experience carried out at 199°C for 12 hours. Pressure N2O when the reaction temperature is 50 ATM. As the oxygen-containing reaction products formed benzaldehyde, acetophenone and phenylacetaldehyde in the approximate molar ratio of 7.5:2:1. Example 17 describes the oxidation of 1-hexene. The experience carried out analogously to example 2 with the difference that as the starting alkene take 25 ml of 1-hexene. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O 70%, and the initial pressure is set to 45 ATM. The experience carried out at 197°C for 12 hours. Pressure N2O when the reaction temperature is 70 ATM. In the reaction, the conversion of 1-hexene is 11%. In the reaction products detected the following oxygen-containing compounds: 2-hexanon (32%), hexanal (30%), pentanal (32%). Example 18 is similar to example 17 with the difference that instead of 1-hexene using 1-octene and the reaction is carried out at 300°C for 2 hours. Pressure N2O when the reaction temperature is 85 ATM. In the reaction, the conversion of 1-octene was 63%. In the reaction products detected the following kolorem difference, what was charged to the reactor 10 g 1 octadecene (C18H36and as a solvent of 15 ml of n-heptane. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2About 20%, and the initial pressure is set to 45 ATM. The experience carried out at 300°C for 2 hours. Pressure N2About under the reaction conditions is 17 ATM. As oxygen-containing products are formed 2-octadecanol, octadecanol and heptadecanol with a total selectivity of 84%. Conversion of 1-octadecene is 24%. Example 20 is similar to example 17 with the difference that was charged to the reactor 25 cm32 nonene (C9H18). In the reactor serves a mixture of nitrous oxide with nitrogen, in which the concentration of N2About 20%, and the initial pressure of the mixture set to 45 ATM. The experience is carried out at 350°C for 2 hours. Pressure N2About under the reaction conditions is 18 ATM. Conversion of 2-nonene is 13.7% for total selectivity education 2-nonanone and 3-nonanone 90,5%. Example 21 is similar to example 17 with the difference that was charged to the reactor 8 g of stilbene and the solvent of 15 ml of toluene. In the reactor serves a mixture of nitrous oxide with nitrogen, in which the concentration of N2About 70%, and the initial pressure of the mixture set to 45 atmospheres. the oradatabase product formed deoxybenzoin (2-phenylacetophenone). Conversion of stilbene amounts to 25.5%. Example 22 is similar to example 17 with the difference that was charged to the reactor 10 g 11-hexadecan-1-yl acetate [CH3(CH2)3CH=CH(CH2)10(AOSN3)] and as a solvent of 15 ml of toluene. In the reactor serves a mixture of nitrous oxide with nitrogen, in which the concentration of2O 40%, and the initial pressure of the mixture set to 40 ATM. The experience carried out at 230°C for 5 hours. Pressure N2O under the reaction conditions is 30 ATM. As oxygen-containing products are formed 12-oxo-hexadecan-1-yl acetate [CH3(CH2)3(C=O)CH2(CH2)10(AOSN3)] and 11-oxo-hexadecan-1-yl acetate [CH3(CH2)3CH2(C=O)(CH2)10(AOSN3)] in the approximate ratio 1:1 with a total selectivity of 90% at a conversion of 11-hexadecan-1-yl acetate to 18.3%. Example 23 is similar to example 22, with the only difference that was charged to the reactor 10 g oleic alcohol [CH3(CH2)7CH=CH(CH2)8IT] as a solvent of 15 ml of mesitylene. The experience carried out at 230°C for 5 hours. Pressure N2O under the reaction conditions is 30 ATM. As oxygen-containing products are formed 1-SUB>3(CH2)7CH2(C=O)(CH2)8HE's] in the approximate ratio 1:1 with a total selectivity of 89% for the conversion of oleic alcohol 16,8%. Example 24 is similar to example 17 with the difference that was charged to the reactor 25 cm35-HEXEN-2-it. In the reactor serves a mixture of nitrous oxide with inert gas - nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor, R0set of 45 ATM. The experience carried out at 220°C for 5 hours. Pressure N2O under the reaction conditions is 72 ATM. As oxygen-containing products are formed 2,5-hexanedione, 5-oxopentanoic and 4-oxopentanoic with a total selectivity 80,4% at a conversion of 5-HEXEN-2-it 24,7%. Example 25 is similar to example 24, with the only difference that was charged to the reactor 25 cm31.7 octadiene. The experience carried out at 220°C for 5 hours. Pressure N2O under the reaction conditions is 72 ATM. The conversion of 1,7-octadiene is 22%. As the main oxygen-containing products are formed 7-octene-2-it, 7-octenyl, 6-heptenal (80%), and 2,7-octandiol, octandiol and 7-oxooctanoate (20%). Examples 2-13 and 15-25 show the possibility of oxidation of aliphatic alkenes to carbonyl compounds with politely leads to the formation of explosive compositions alkene-N2Oh in the gas phase when filling the reactor with nitrogen oxide, heat or reaction conditions. For example, the process of example 1 without the addition of inert gas leads to the formation of mixtures containing up to 16.5% vapor alkene in nitrous oxide, the explosion of which are described in [G. Panetier, A. Sicard, V Symposium on Combustion, 620 (1955); B. B. Brandt, L. A. Matov, A. I. Raslowsky, C. S. Khailov, Chem. prom., 1960, No. 5, S. 67-73]. The process under similar conditions, but using a mixture of N2O-inert gas in which the concentration of N2O is 20% (example 2), allows to avoid the formation of explosive mixtures and to ensure the safety of the process. According to the proposed method, the content of N2O in an inert gas may vary widely, including in the area of concentration of nitrous oxide 25% or less, which excludes the possibility of hazardous situations at all stages of the process when all the compositions with the alkene. As shown by examples 2, 9, 19 and 20, the oxidation reaction in this area proceeds with high efficiency. In the present invention, a method for obtaining carbonyl compounds, based on the reaction of liquid-phase oxidation of aliphatic alkenes WITH2- 1. The method of obtaining carbonyl compounds with the number of atoms2-C40carried out by contact with nitrous oxide in the liquid phase of aliphatic alkenes WITH2-C40formula where R1, R2, R3, R4radicals that can be represented by atoms of hydrogen, alkyl, alkenylamine or aryl radicals, including those containing functional groups, in addition to radicals, which include in their composition nonaromatic carbocycle, having in its composition a double bond C=C, characterized in that the reaction is carried out at a temperature of 100-3500And pressure of nitrous oxide 1.5 to 100 atmospheres in the presence of an inert gas diluent. 2. The method according to p. 1, in which the concentration of inert gas in the reaction mixture does not exceed 99%. 3. The method according to any of paragraphs.1 and 2, in which the concentration of the inert gas is selected so that the content of N2O in a mixture with inert gas was not more than 25% to avoid the formation of explosive compositions at all stages of the process. 4. The method according to any of paragraphs.1-3, in which the reaction is carried out in the presence of a catalyst. 5. The method according to any of paragraphs.1-4, in which
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