7-c20
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A method of obtaining a monocyclic ketones7-c20

A method of obtaining a monocyclic ketones<sub>7</sub>-c<sub>20</sub>
IPC classes for russian patent A method of obtaining a monocyclic ketones7-c20 (RU 2227136):
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(57) Abstract:

The invention relates to a method for producing monocyclic ketones7-C20. The method consists in the oxidation of monocyclic alkenes of the formula CnH2ncontaining 7-20 carbon atoms in the cycle, corresponding monocyclic ketones 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 product, the explosion of work and is promising for industrial applications. 1 S. and 4 C. p. F.-ly, 5 PL.

The invention relates to a method for producing monocyclic ketones7-C20more specifically the way they are received by the liquid-phase oxidation of nitrous oxide (N2O) monocyclic alkenes of the formula CnH2n-2containing 7-20 carbon atoms.

Monocyclic ketones7-C20are important intermediate products in the synthesis of various organic compounds, including dicarboxylic acids and lactams. The latter are used for the production of a variety of luminescent materials, for example nylon-8, nylon-12, and others.5-C12in the mixture of the corresponding cyclic ketones and alcohols in the presence of salts of Co, MT, si, Fe, Ni. The process is conducted at 130-160°C, a pressure of 5-25 ATM and conversion of 3-6%.

A common drawback of these methods is the formation along with ketones, significant amounts of cyclic alcohols, as well as a sharp drop in the selectivity of the reaction with increasing conversion.

In the patent GB Pat. 649, 680 (1951) claimed method oxidation of olefins to carbonyl compounds nitrous oxide. According to the main drawback 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 N2About almost as explosive as the 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 a monocyclic ketones7-C20 by oxidation of 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 nezhelatelno, as it can result in a loss of selectivity due to the contribution of gas-phase oxidation.

Explosion-proof usloviyah reaction with N2O, for example nitrogen, argon, helium, 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 process safety it is advisable to have this dilution nitrous oxide inert gas to the reaction mixture was explosive 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 monocyclic alkenes to ketones can be carried out in a wide range of conditions both in static and flow-through reactor, which may be made of steel, titanosauria efficiency of gas-liquid reactions.

In the case of a static variant of the process in the autoclave at room temperature load monocyclic alkene in such quantity that when heated to the reaction temperature, he was present as a liquid phase. Then, serves a mixture of nitrous oxide with inert gas, reducing 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 closed and heated to the reaction temperature in the region of 20-350°C. the reaction Time depends on the environment and requirements of process indicators, 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 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 polycrystalline as in pure form, and with admixtures of various gases, not having a harmful effect on process performance. Monocyclic alkenes WITH7-C20may also contain traces of other organic compounds, 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 cm cyclooctene (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, measure pressure 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 cyclooctene (X) and selectivity of the reaction cyclooctanone (S):

the concentration of cyclooctanone in the reaction products;WITHside- total concentration of by-products. In the case of large conversion value X can be calculated also by the difference between the initial and final concentrations cyclooctene:

Conversion cyclooctene and selectivity of the reaction cyclooctanone shown in the 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 N2O is 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.

This example shows that the reaction of the liquid-phase oxidation of 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 C is receiving, 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 100With over 100 hours Pressure N2About 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 10 h 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 12 hours Pressure N2About 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 3 hours Pressure N2O at a temperature of react the nitrogen is 40%, and the initial pressure of the mixture set to 40 ATM. Pressure N2O when the reaction temperature is 31 ATM.

Example 8 is similar to example 2 with the difference that the initial pressure of the mixture of N2O and nitrogen in the reactor is set to 45 ATM. The experience carried out at 220°C for 12 hours Pressure N2O when the reaction temperature is 15 ATM.

Example 9 same as example 6 with the difference that the initial pressure in the reactor was set to 30 ATM. The experience is carried out at 350°C for 2 h Pressure N2O when the reaction temperature is 55 ATM.

Example 10 same as example 2 with the difference that for the oxidation of a mixture of nitrous oxide and argon, in which the concentration of N2O is 50%. The initial pressure in the reactor was set to 30 ATM. The experience carried out at 220°C for 12 hours Pressure N2O when the reaction temperature is 30 ATM.

Example 11 same as example 10 with the difference that instead of argon using carbon dioxide.

Example 12 same as example 6 with the difference that the initial pressure of the mixture in the reactor set 53 ATM. The experience carried out at 180°C for 12 hours Pressure N2O when the reaction temperature is 75 ATM.

Examples 14-15.

These examples (PL.3) demonstrate the ability to conduct the process in the presence of a catalyst.

Example 14 same as example 12 with the difference that the reaction of the lead 6 h in the presence of 0.2 g Fe2O3/SiO2(2.8 wt.% Fe2O3). The catalyst is prepared by impregnation of SiO2solution Fl3, dried at 110°C and calcined in air at 500°C for 2 hours To oxidize a mixture of nitrous oxide with nitrogen, in which the concentration of N2O is 70%. The initial pressure in the reactor set 53 ATM. The experience carried out at 180°C. the Pressure of N2O when the reaction temperature is 75 ATM.

Example 15 same as example 14 with the difference, Croom AgNO3, dried at 110°C and calcined in air at 500°C for 2 h

Examples 16-19.

These examples demonstrate the possibility of oxidation cyclooctene in the presence of various solvents (table.4).

Example 16 same as example 12 with the difference that in the reactor pour 25 ml of a mixture of cyclooctene and cyclohexane in a volume ratio of 1:1.

Example 17 same as example 16 except that instead of using cyclohexane acetonitrile.

Example 18 is similar to example 16 with the difference that instead of cyclohexane using isobutyl alcohol.

Example 19 is similar to example 16 with the difference that instead of cyclohexane using cyclooctane.

Examples 20-21.

Examples 20-21 show the possibility of oxidation of cycloheptene and cyclododecene in cyclic ketones using mixtures of nitrous oxide with inert gases (PL.5).

Example 20 is similar to example 12 with the difference that instead of cyclooctene use cyclohepten.

Example 21 is similar to example 6 with the difference that instead of cyclooctene use skatyvajut, what 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-N2O 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 14.5% of vapor cycloalkene 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 nitrous oxide in a mixture with an inert gas can vary widely, including in the area of concentrations of N2O 25% or less, which excludes the possibility of hazardous situations at all stages of the process when any component is efficiency.

In the present invention proposed a new method for producing monocyclic ketones7-C20based on the reaction of liquid-phase oxidation of 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. A method of obtaining a monocyclic ketones7-C20carried out by contact of nitrous oxide in the liquid phase with a monocyclic alkenes of the formula CnH2n-2containing 7-20 carbon atoms in the cycle, characterized in that the reaction is carried out at a temperature of 100-3500And pressure of N2O 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

 

 

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