The method of obtaining substituted monocyclic ketones |
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IPC classes for russian patent The method of obtaining substituted monocyclic ketones (RU 2227134):
C07C49/487 -
C07C49/385 -
       
 The method of obtaining carbonyl compounds / 2227133
The invention relates to a method for producing carbonyl compounds with the number of atoms2-C40
 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.
 1-hydroxyadamantanon-4-one preparation method / 2319688
Invention provides a method for preparation of 1-hydroxyadamantanon-4-one (Kemantan), which can be used as immunostimulating drug effective to treat vascular system diseases, limbs autoimmune genesis extremities, tuberculosis, infection-allergic bronchial asthma, chronic aphthous stomatitis, herpes, as well as anticataleptic agent and intermediate for synthesis of 1,4-bifunctional derivatives of adamantane. Method comprises oxidation of adamantanone by means of sulfuric/nitric acid mixture in the form of complex oxidation-activating system including sulfuric, nitric, and acetic acids, molar ratio adamantanone/sulfuric acid/nitric acid/acetic acid being 1: (1.75) : (8.43-12.62) : (0.25-1). Process is carried out when stepwise raising temperature: first, at 35°C, nitric acid is measured out to reaction mass for 1-1.5 h, after which temperature is raised to 50-55°C for 12-16 h.
 Method of producing 1-acetyl-4- propionylbenzene / 2374217
Invention relates to a method of producing 1-acetyl-4-propionylbenzene, which is starting material for making medicinal agents and dipyrrolylbenzenes, used in synthesis of conducting interlinked polymer systems, which can be used as electrode materials for energy accumulators, biosensors, photoluminescent materials, electroluminescent materials and electromagnetic shields. The method involves using propionyl chloride and ethylbenzene as starting material in an organic solvent medium, and carrying out the reaction in the presence of anhydrous aluminium chloride at temperature between 25 and 40°C for 20 to 60 minutes, with formation of an intermediate product 1-propionyl-4-ethylbenzene, which is separated and oxidised with potassium permanganate in an aqueous solution of magnesium nitrate at temperature between 65 and 80°C for 3 to 5 hours, forming the desired product which is extracted using toluene, with subsequent recrystallisation from n-hexane or petroleum ether. The method uses non-toxic and readily available components, which makes the proposed method suitable for industrial use.
 4,4'-difluorobenzophenone synthesis method / 2394016
Present invention relates to a method for synthesis of 4,4'-difluorobenzophenone, the main raw product for synthesis of aromatic polyester-ketones. The method involves a first step where fluorobenzene reacts with formaldehyde under conditions for catalysis with organic sulphonic acids to form difluorodiphenylmethane. The product is extracted and oxidised with nitric acid at the second step to 4,4'-difluorobenzophenone.
 Method of producing acrolein, acrylic acid or mixture thereof from propane / 2429218
According to method A) an input stream of the reaction gaseous mixture A is fed into the input of the first reaction zone A, where the input stream is obtained by merging at least four different gaseous initial streams 1, 2, 3 and 4, where the gaseous initial streams 1 and 2 contain propane, gaseous initial stream 4 is molecular hydrogen and gaseous initial stream 3 is fresh propane, the input stream of the reaction gaseous mixture A is passed at least through one catalyst layer of the first reaction zone A on which, if needed, when feeding other gaseous streams, as a result of heterogeneous catalytic partial dehydrogenation of propane, a stream of products of gaseous mixture A forms, which contains propane and propylene, the stream of products of gaseous mixture A comes out of the first reaction zone A through the corresponding outlet, while splitting said stream into two partial streams 1 and 2 of products of the gaseous mixture A with identical composition, and the partial stream 1 of products of the gaseous mixture A is returned to the first reaction zone A as the gaseous initial stream 1, the partial stream 2 of products of the gaseous mixture A, if needed, is directed to the first separation zone A, in which a portion or more of components contained therein, which are different from propane and propylene, are separated, as a result of which a stream of products of gaseous mixture A' which contains propane and propylene, B) partial stream 2 of products of the gaseous mixture A or a stream of products of gaseous mixture A' is used in a second reaction zone B for supplying at least one oxidation reactor, in which propylene contained in the partial stream 2 of products of gaseous mixture A or in the stream of products of gaseous mixture A' undergoes selective heterogeneously catalysed partial gas-phase oxidation with molecular oxygen to obtain a stream of products of a gaseous mixture B, which contains acrolein, acrylic acid or mixture thereof as the desired product, unconverted propane and, if needed, unconverted propylene, as well as molecular oxygen, the stream of products of gaseous mixture B comes out of reaction zone B, the desired product contained in separation zone B is separated in said separation zone B and at least a portion of residual gas formed after separation and containing unconverted propane, molecular oxygen and, if needed, unconverted propylene, is returned to reaction zone A as gaseous initial stream 2. Gaseous initial streams 2, 3 and 4 as well as, if needed, additional gaseous initial streams different from the gaseous initial stream 1, are merged into a gaseous stream of the working mixture, after which, using this gaseous stream of the working mixture as the working stream, a jet pump is activated, said pump having a nozzle, a mixing section, a diffuser and a suction inlet. Movement of the working stream which is throttled through the nozzle, the mixing section and the diffuser to the input of the first reaction zone A, as well as the suction effect of the suction inlet takes place in the direction of outlet of the stream of products of gaseous mixture A from the first reaction zone A. The pressure drop created in the suction nozzle with splitting of the stream of products of the gaseous mixture A into two partial streams 1 and 2 results in suction of the partial stream 1 of products of the gaseous mixture A, its movement through the diffuser with simultaneous mixture with the working stream on the mixing section and inlet of the formed reaction stream of gaseous mixture A at its inlet point into the first reaction zone A, characterised by that a gaseous initial mixed stream is formed first by merging in random sequence gaseous initial streams 2 and 3, as well as, if needed, additional gaseous initial streams different from gaseous initial streams 1 and 4, and only after that the gaseous initial stream 4 is added to the formed gaseous initial mixed stream to obtain a gaseous mixed working stream.
 Method of conducting continuous process of producing acrolein, acrylic acid or mixture thereof from propane in stable operating mode / 2429219
Invention relates to a method of conducting a continuous process of producing acrolein, acrylic acid or mixture thereof from propane in a stable operating mode, according to which: A) propane in a first reaction zone A undergoes heterogeneously catalysed dehydrogenation in the presence of molecular oxygen to obtain a gaseous mixture of products A containing propane and propylene, B) the gaseous mixture of products A, if needed, is fed into a first separation zone A in which a portion or more of components different from propane and propylene is separated therefrom and a gaseous mixture of products A' containing propane and propylene remaining after separation is obtained, C) the gaseous mixture of products A or gaseous mixture of products A' is fed into at least one oxidation reactor of the second reaction zone B, in which propylene contained therein undergoes partial selective heterogeneously catalysed gas-phase oxidation with molecular oxygen to obtain a gaseous mixture of products B, which contains acrolein, acrylic acid or mixture thereof as the desired product, unconverted propane, excess molecular oxygen and, if needed, unconverted propylene, D) in the second separation zone B, the desired product contained therein is separated from the gaseous mixture of products B, and at least a portion of the remaining gas containing propane, molecular oxygen and, if needed, unconverted propylene is returned to the reaction zone A as circulation gas 1 containing molecular oxygen, E) fresh propane is fed into at least one continuous flow process zone selected from a group comprising reaction zone A, separation zone A, reaction zone B and separation zone B, where the said fresh propane is fed at a rate characterised by a given stationary value when realising the process in a stable operating mode, and F) content of molecular oxygen in the gaseous mixture of products B is continuously determined and said value is compared with the desired stationary value needed to realise the process in stable operating mode, characterised by that if at a certain moment in time, content of molecular oxygen in the gaseous mixture of products B exceeds the given desired stationary value, fresh propane is fed into the process right away at feed rate higher than its stationary value, and if at a certain moment in time, content of molecular oxygen in the gaseous mixture of products B is lower than the corresponding given desired stationary value, fresh propane is fed into the process right away at feed rate lower than its stationary value.
Method for direct conversion of lower c1-c4 paraffins to oxygenates / 2485088
Invention relates to a method for direct conversion of lower C1-C4 paraffins to oxygenates such as alcohols and aldehydes, which are valuable intermediate products of organic synthesis and can be used as components of engine fuel and/or starting material for producing synthetic gasoline and other engine fuels. The method involves passing a mixture consisting of a lower paraffin or oxygen, diluted with an inert gas or air or pure oxygen, through a catalyst bed at temperature not higher than 350°C. The catalyst used is a catalyst system for heterogeneous reactions, which contains microfibre of a high-silica support and at least one active element, the active element being in form of either a MeOxHalv composite or a EwMezOxHaly composite, wherein the element Me in both composites is selected from a group which includes transition metals of groups 5-12 and periods 4 and 5, or elements of lanthanum or lanthanide groups or, preferably, ruthenium; element Hal is one of the halogens: fluorine, chlorine, bromine, iodine, but preferably chlorine; element E in the EwMezOxHaly composite is selected from a group which includes alkali, alkali-earth elements, or hydrogen, and indices w, z, x and y are weight fractions of elements in given composites and can vary in the following ranges: z - from 0.12 to 0.80, x - from 0.013 to 0.34, y - from 0.14 to 0.74, w - from 0 to 0.50.
Method of vanillin manufacturing / 2519550
Method consists in air oxygen oxidation of lignin, obtained by fermentative hydrolysis of wood of coniferous species or wood, affected by brown or mottled rot, with content of lignin 40-90 wt % in water-alkali medium at higher temperatures and pressure. The process is carried out in presence of catalysts on the basis of copper hydroxide with continuous supply of alkali solution into reactor for 1-150 minutes.
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(57) Abstract: The invention relates to a method for producing substituted monocyclic ketones4-C20. The method is based on the reaction of liquid-phase oxidation of substituted monocyclic alkenes of the formula CnH(2n-2-m)Rimwhere n has a value from 4 to 20, m has a value from 1 to (2n-2), Rithe meaning of the substituents in the cycle that represent a hydrogen atom, alkyl, alkeline or aryl radicals, including those containing functional groups, in addition to radicals which comprise non-aromatic Carbo - or heterocyclic compounds having a double bond C=C, 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. 1 S. and 4 C.p. f-crystals, 3 tables. The invention relates to a method for producing substituted monocyclic ketones4-C20more specifically to the way they are received by the liquid-phase oxidation of nitrous oxide (N2O) substituted monocyclic alkenes containing 4-20 carbon atoms in the cycle is and a variety of organic products, including synthetic polymeric materials, agrochemicals, pharmaceuticals, etc. There are several ways of obtaining substituted monocyclic ketones. For example, for this purpose, widely used liquid-phase oxidation of alkyl substituted cycloalkanes oxygen. The oxidation may be carried out in the presence of a catalyst and without catalyst. In both cases, as the reaction products formed by the mixture of cyclic ketones and alcohols. For example, mono - and dialkylamino cycloalkanes C5-C8oxidized by non-catalytic in the mixture of the corresponding ketones and alcohols at a temperature of 150-210°C and the pressure 3-40 ATM. In the case of methylcyclohexane a mixture is formed of methylcyclohexanone and 3-methylcyclohexanol, in which the proportion of ketones is about 50% [US Pat. No. 2609395, 1952, C. F. Doungherty et al.]. A mixture of alkyl substituted cyclic ketones and alcohols can also be obtained from the relevant cycloalkenes using as catalyst and salts From MP at 120-180°C and a pressure of 5-25 ATM [US Pat. No. 2223494, 1940, J. Loder; US Pat. No. 3093686, 1963, W. Simon et al.; US Pat. No. 3917708, 1975, A. Kuessner et al.]. A common drawback of these methods is the formation along with a ketone, a large number cyclization monocyclic ketones can be obtained by decarboxylation and cyclization alkyl substituted dicarboxylic acids [US Pat. 5600013, 1997, Alas et al.]. The process is conducted at 200-300°C, using as catalysts phosphates of metals 1A, 2A or 3b groups of the periodic system of elements. So, from 2,2-dimethyladipate acid in the presence of sodium phosphate is formed 2,2-dimethylcyclopentane. In addition to the high cost of raw materials the disadvantage of this method is the presence of aggressive acidic environment at high temperature. According to the patent [US Pat. No. 2863923, 1958, N. M. Bortnick] 2,5-dimethylcyclopentane can be obtained by cyclization of esters of 2,5-dimethyladipate acid at 350-600°C in the presence of oxides MP or Cd. The disadvantage of this method is the need for an additional stage of obtaining esters, which complicates the technological scheme. A method of obtaining monocyclic ketones containing a methyl group in -position, by alkylation of the corresponding cyclic ketones with methanol at 350-500°C in the presence of Mn oxide [US Pat. No. 4618725, 1986, H. H. Lenz]. However, the selectivity of this reaction is not high enough.
In the patent GB Pat. 649680 (1951) claimed method oxidation of olefins to carbonyl compounds nitrous oxide. According to this method, in particular, obtaining a 2-metallicum oxidation of 1-phenylcyclohexene.
The main disadvantage of this method is the possibility of formation of flammable mixtures “cycloalken nitrous oxide” during the process. 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 as explosive as a mixture of olefins [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]. Therefore, saturated hydrocarbons, in spite of their lower reactivity, can not serve as a means to avoid the explosion.
This patent discloses a method of obtaining substituted monocyclic ketones by oxidation of substituted monocyclic alkenes with nitrous oxide, N2O, 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 an inert gas under conditions when cycloalken 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, as it can periodicities alkenes is expressed by the formula
where Riidentical or different substituents in the loop, n has a value from 4 to 20, m has a value from 1 to (2n-2). The substituents Riin the formula (I) can be represented by atoms of halogen, alkyl, alkenylamine, aryl, or other inorganic or organic radicals, including those containing functional groups, in addition to radicals which comprise non-aromatic Carbo - or heterocyclic compounds having a double bond C=C. for Example, in the case methylcyclohexene the radical Rirepresented by a group of CH3, n=6, m=1.
Intrinsically safe working conditions for the proposed method are provided by adding to the reaction mixture an inert gas reacts with N2O, for example nitrogen, helium, argon, carbon dioxide, etc. or their mixture. The role of the inert gas can play the off-gases reaction or recirculating gases. At different stages of the process, depending on the ratio of cycloalken: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 security protivootechnoy by any content of cycloalkene. This condition is satisfied if the content of N2O in a mixture with an inert 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 substituted monocyclic alkenes C4-C20into corresponding cyclic 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 methods that increase the efficiency of gas-liquid reactions.
In the case of a static option in the autoclave put cycloalken in such quantity 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 picked ESI with nitrous oxide picked so to no more than 99%. Then the reactor is closed and 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 can vary from several tens minutes to several tens of 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 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.
The proposed method does not involve high purity reagents. So, nitrous oxide can be used both in pure form and mixed with various gases, not having a harmful effect on process performance. Substituted monocyclic alkenes may also contain traces of other organic compounds, especially if they do not contain double C=C bonds.
The essence of the invention is illustrated by the following examples.
Examples 1-2
Example 1. This example is cf), pour 25 cm34-methyl-1-cyclohexene (Aldrich, 99%). The reactor is rinsed with nitrogen and then brought her pressure up to 10 ATM. The reactor was sealed, heated to 220°C and kept at this temperature for 12 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 phase methods, gas chromatography, gas chromatography / mass spectrometry and NMR. From the obtained data to calculate the conversion of 4-methyl-1-cyclohexene (X) and selectivity of the reaction for forming the products (Si)
where Cithe concentration of the i-th reaction product, - the initial concentration of 4-methyl-1-cyclohexene. In the case of large conversion value X can be calculated also by the difference between the initial and final concentrations of 4-methyl-1-cyclohexene
The main products of the reaction are 3-methylcyclohexanol and 4-methylcyclohexanone. In the likesto.
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 N2O is 20% (table.1).
The initial pressure of the mixture in the reactor, R°, set to 90 ATM. The pressure of nitrous oxide when the reaction temperature is 30 ATM.
This example shows that the reaction of the liquid-phase oxidation of substituted monocyclic alkenes in cyclic ketones proceeds with retention of conversion and high selectivity when used as an oxidizer mixtures of nitrous oxide with inert gas.
Examples 3-10
Examples 3-10 show the possibility of carrying out the reaction using mixtures of nitrous oxide with inert gases of different composition (table.2).
Example 3 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 70%, and the initial pressure in the reactor was set to 80 ATM. The experience carried out at 100 C for 90 hours. Pressure N2O when the reaction temperature is 100 ATM.
Example 4 same as example 2 with the difference that nachalnoy the pressure of the mixture in the reactor was set to 100 ATM. The experience carried out at 250°C for 24 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 198°C for 15 hours. Pressure N2O when the reaction temperature is 70 ATM.
Example 6 same as example 2 with the difference that the concentration of N2O in a mixture with nitrogen is 70%, and the initial pressure of the mixture in the reactor was set to 45 ATM. The experience carried out at 250°C for 5 hours. Pressure N2O when the reaction temperature is 77 ATM.
Example 7 same as example 6 with the difference that the concentration of N2O in the mixture is 20%. The experience carried out at 250°C for 12 hours. Pressure N2O when the reaction temperature is 15 ATM.
Example 8 is similar to example 2 with the difference that for the oxidation of a mixture of nitrous oxide and argon, in which the concentration of N2About 50%. The initial pressure of the mixture in the reactor was set to 30 ATM. Pressure N2O when the reaction temperature is 30 ATM.
PR is similar to example 7 with the difference, that experience carried out at 350°C for 2 hours. Pressure N2O when the reaction temperature is 20 ATM.
Example 11
This example is comparative. The experience carried out analogously to example 6 with the difference that was charged to the reactor 3 ml of 4-methyl-1-cyclohexene. If you prefer the entire 4-methyl-1-cyclohexen under the reaction conditions is in the gas phase. The experience carried out at 250°C for 5 hours using a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. Experience the conversion of 4-methyl-1-cyclohexene was about 0.5%. This shows that under these conditions the reaction in the gas phase is hardly taking place.
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 5 with the difference that the oxidation of 4-methyl-1-cyclohexene is carried out in the presence of 0.5 g of Fe2ABOUT3/SiO2(2.8 wt.% Fe2O3). The catalyst is prepared by impregnation of SiO2a solution of FeCl3, dried at 110°C and calcined in air at 500°C for 2 hours. To OK the giving of the mixture in the reactor set 28 ATM. The experience carried out at 198°C for 15 hours. Pressure N2O when the reaction temperature is 70 ATM.
Example 13 same as example 5 with the difference that the reaction is carried out in the presence of 0.3 g of Ag/SiO2(1 wt.% Ag). The catalyst is prepared by impregnation of SiO2 a solution of AgNO3, dried at 110°C and calcined in air at 500°C for 2 hours.
Examples 14-15
These examples demonstrate the possibility of oxidation of 3-cyclohexen-1-yl-methanol and 5-methylcyclohexane-1 using nitrous oxide, diluted with an inert gas, including with the use of solvents.
Example 14 same as example 6 with the difference that in the reactor pour 25 cm3a mixture of 3-cyclohexen-1-methanol and cyclohexane in the volume ratio 1:1, and the experience is carried out at 150°C for 20 hours. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. Pressure N2O when the reaction temperature is 60 ATM. Conversion of 3-cyclohexen-1-methanol is 2.5%. The reaction proceeds with the formation of 3-oxocyclohexyl-1-methanol and 4-oxocyclohexyl-1-methanol is one, instead of 4-methyl-1-cyclohexene using 5-methyl-cycloocten-1, and the experience carried out at 198°C for 12 hours. Pressure N2O when the reaction temperature is 70 ATM. Conversion of 5-methylcyclohexane-1 is 30,5%. As a result of reaction formed 4-methylcyclohexanone and 5-Methylcyclopentane in the ratio of 1:1 with a total selectivity of 95%.
Examples 16-17
These examples demonstrate the possibility of oxidation of 1-methyl-1-cyclohexene using nitrous oxide, diluted with an inert gas, including the use of solvents.
Example 16 same as example 6 with the difference that in the reactor pour 25 cm31-methyl-1-cyclohexene (Aldrich, 99%), and the experience is carried out at 250°C for 12 hours. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. Pressure N2O when the reaction temperature is 77 ATM. Conversion of 1-methyl-1-cyclohexene is 35% with a total selectivity of formation of 2-methylcyclohexanone series and cyclopentadecanone (in the approximate ratio 1:1) 79%.
Example 17 same as example 16 except that the reactor is poured 70 cm3a mixture of 1-methyl-1-cyclohexene is I N2O is 40%. The initial pressure of the mixture in the reactor was set to 40 ATM. Pressure N2O when the reaction temperature is 38 ATM. Conversion of 1-methyl-1-cyclohexene is 22% for total selectivity of formation of 2-methylcyclohexanone series and cyclopentadecanone of 80.3%.
Examples 18-26
These examples demonstrate the possibility of oxidation with nitric acid diluted with an inert gas, including using solvents of different substituted monocyclic alkenes, including as Vice-atoms of halogen, various functional groups, alkyl, alkeline or aryl (including heterocyclic) radicals.
Example 18 is similar to example 6 with the difference that was charged to the reactor 25 cm31-methyl-1-cyclopentene and experience is carried out at 198 C for 10 hours. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. Pressure N2O when the reaction temperature is 70 ATM. As oxygen-containing products are formed 2-methylcyclopentanone and 1-HEXEN-5-non in the approximate ratio of 1.5:1 with smeru 6 with the difference, what was charged to the reactor 25 cm 3-bromocyclohexene and experience is carried out at 198°C for 12 hours. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. Pressure N2O when the reaction temperature is 70 ATM. As oxygen-containing products are formed 2-bromocyclohexane and 3-bromocyclohexene in the approximate ratio 1:1 with a total selectivity of 84%. Conversion of 3-bromocyclohexene is 6%.
Example 20 analogous to example 19, with the only difference that was charged to the reactor 25 cm33-cyclohexen-1-carboxaldehyde and benzene in a volume ratio of 1:1. Conversion of 3-cyclohexen-1-carboxaldehyde is 8.8% for total selectivity education (cyclohexanone-3-yl)carboxaldehyde and (cyclohexanone-4-yl)carboxaldehyde 85,6%.
Example 21 analogous to example 19, with the only difference that was charged to the reactor 25 cm33-cyclohexen-1-ol. As oxygen-containing products are formed 3-hydroxycyclohexanone and 4-hydroxycyclohexanone in the approximate ratio 1:1 with a total selectivity of 84% conversion C-cyclohexen-1-ol 5,6%.
Example 22 is similar to example 19 with the s form 3-ethynyl-1-cyclohexanone, 4-ethynyl-1-cyclohexanone, 3-cyclohexen-1-carboxaldehyde, 1-(3-cyclohexen-1-yl)Etalon and 3-cyclohexen-1-acetaldehyde with a total selectivity of 73% for the conversion of 4-vinylcyclohexane of 10.5%.
Example 23 analogous to example 19, with the only difference that was charged to the reactor 25 cm31,3,5-trimethyl-1-cyclohexene, and the experience is carried out at 220With in 12 hours. Pressure N2O when the reaction temperature is 72 ATM. As oxygen-containing products are formed 2,4,6-trimethylcyclohexane and 1-(2,4-dimethyl)cyclopentylamine in the approximate ratio of 1.4:1 with a total selectivity 80,4% conversion of 1,3,5-trimethyl-1-cyclohexene 17,5%.
Example 24 is similar to example 6 with the difference that was charged to the reactor 25 cm36-methyl-3-cyclohexen-1-methanol. For oxidation of a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure of the mixture in the reactor was set to 45 ATM. The experience carried out at 250°C for 5 hours. Pressure N2O when the reaction temperature is 77 ATM. Conversion of 6-methyl-3-cyclohexen-1-methanol is 16.7%. The reaction proceeds with the formation of 2-methyl-4-oxocyclohexyl-1-methanol and 2-methyl-5-oxocyclohexyl-1-metrojaya 25 cm34-(3-cyclohexen-1-yl)pyridine. Conversion of 4-(3-cyclohexen-1-yl)pyridine 15.7%. The reaction proceeds with the formation of 4-(3-cyclohexanone-1-yl)pyridine and 4-(4-cyclohexanone-1-yl)pyridine with a total selectivity of 97%.
Example 26 is similar to example 24, with the only difference that was charged to the reactor 25 cm31-phenyl-1-cyclohexene. Conversion of 1-phenyl-1-cyclohexene is 12.6%. The reaction proceeds with the formation of 2-phenylcyclohexanone and cyclopentanedione with a total selectivity of 91%.
Examples 2-10 and 12-26 show that substituted monocyclic alkenes with high selectivity are oxidized to the corresponding ketones using nitrous oxide, diluted with an inert gas. The process without the use of an inert gas diluent leads to the formation of explosive compositions cycloalken-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 15% 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., 1 the Torah 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 cycloalkenes. As shown by examples 2, 7 and 10, the oxidation reaction in this area proceeds with high efficiency.
In the present invention proposes a new method of obtaining substituted monocyclic ketones, based on the reaction of liquid-phase oxidation of substituted monocyclic alkenes with a mixture of nitrous oxide with inert gas. The process provides high selectivity, the explosion and is promising for industrial applications.
1. The method of obtaining substituted monocyclic ketones, carried out by contact with nitrous oxide in the liquid phase substituted monocyclic alkenes of the formula where n has a value from 4 to 20, m has a value from 1 to (2n-2), where Ri- deputies in the cycle, which can pythonconsole group, in addition to the radicals, which comprise non-aromatic Carbo - or heterocyclic compounds having a double bond C=C, wherein the reaction is carried out at a temperature of 100-3500And pressure of N2O from 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 the reaction is carried out in the presence of a solvent.
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