Method of obtaining cyclohexylalkylketones

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining saturated aliphatic ketone, represented by the general formula (2), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a cyclohexyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), applied as an initial material for the production of medications, agrochemical preparations, optic functional materials and functional materials for electronics. The method consists in hydrogenation of a nucleus of an aromatic ketone, represented by the general formula (1), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a phenyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), with hydrogen under pressure in the presence of a solvent at a temperature from 20 to 120°C and in the presence of a catalyst, which carries from 0.1 to 20 wt % of the ruthenium atom on a carrier.

EFFECT: method makes it possible to obtain the target product with high selectivity.

6 cl, 24 ex

 

The scope of the invention

The present invention relates to excellent in selectivity method for producing a saturated aliphatic ketone having a cyclohexane ring (sometimes referred to as cyclohexylethylamine)used as starting materials for the production of drugs, agrochemical means, optical functional materials and functional materials for electronics.

Background of invention

Still as way of cooking cyclohexylmethanol was known way of getting them out of the Grignard reagent synthesized from bromocyclohexane, and chloride of the fatty acid (see non-patent document 1). Also known is a method of obtaining them through synthesis of cyclohexanecarbonitrile, followed by reaction with ethylbromide (see non-patent document 2). However, the above-mentioned method of the prior art is associated with some complications, consisting in the fact that the process is long, and disposal of waste, such as metal salts and others, is difficult. In addition, when the aromatic ketone hydronaut hydrogen under pressure according to the method of the prototype (see non-patent document 3), the disadvantage of this method is that the recovery of the carbonyl group of Sintesi is described not cyclohexylethylamine, and aliphatic alcohols or alkylcyclohexane. Further, patent document 1 describes a method of obtaining cyclohexylethylamine in which tsiklogeksilnogo the group has an alkyl substituent in the hydrogenation of phenylalkylamine, in which the phenyl group has an alkyl substituent; however, the yield in this process is approximately 30% or less.

The documents of the prior art

Patent documents

Patent document 1: GP A 61-260 .032

Non-patent documents

Non-patent document 1: Rouzaud J., et al., Bull. Soc. Chim. Fr., 1964, 2908-2916

Non-patent document 2: Doucet, Rumpf, Bull. Soc. Chim. Fr., 1954, 610-613

Non-patent document 3: Elwin E. Harris, James D Lanni and Homer Adkins, J. Am. Chem. Soc., 60, 1938, 1467-1470

The invention

Tasks that should be solved by the invention of

The aim of the present invention is to offer a more technological way to get cyclohexylacetate, which solves the problems regarding the recovery process and output of waste, such as metals and others, and which has high selectivity in the hydrogenation of the nucleus.

Solutions to problems

The authors of the present invention have studied in more technological way to get cyclohexylacetate and as a result have found that when an aromatic ketone hydronaut the core of hydrogen under pressure is the group in the presence of a catalyst, which is the atom of ruthenium, you can get cyclohexylacetate, at the same time keeping it a structure of carbonyl group, and came to the present invention.

Specifically, the present invention relates to a method for producing a saturated aliphatic ketone, in which the aromatic ketone represented by the General formula (1), hydronaut the core of hydrogen under pressure in the presence of a solvent at a temperature of from 20 to 120°C in the presence of a catalyst, which is from 0.1 to 20 wt%. atom of ruthenium on a carrier and thereby gain cyclohexylacetate represented by the General formula (2).

Chemical formula (1):

(1)

(in the chemical formula (1) n indicates an integer from 1 to 3; R represents a hydroxyl group, phenyl group, alkyl group having from 1 to 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms);

Chemical formula (2):

(2)

(in the chemical formula (2), n indicates an integer from 1 to 3; R represents a hydroxyl group, tsiklogeksilnogo group, alkyl group having from 1 is about 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms).

The effect of the invention

According to the method according to the invention cyclohexylacetate can be obtained technologically efficient way, having a high selectivity of the hydrogenation of the nucleus.

The method of carrying out the invention

Aromatic ketone

Aromatic ketone for use as starting material in the invention is a disubstituted aromatic compound, in which, as shown in the General formula (1), hydroxyl group, phenyl group, an alkyl group having from 1 to 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms, attached in the form of R to the aromatic group in addition to attached to it acyl group. From the point of view of selectivity obtain the intended product without hydrogenation of acyl groups are preferred as R is a hydroxyl group, phenyl group or acyl group represented by the following General formula (3).

Chemical formula (3):

(3)

(in the General formula (3) indicates an integer from 1 to 3).

In the General formula (1) n indicates an integer from 1 to 3, and from the point of view of processing the soybean is inane in the process preferably n is 1 or 2.

As the aromatic ketone represented by the General formula (1)can be given as a specific example, p-hydroxyacetophenone, m-hydroxyacetophenone, o-hydroxyacetophenone, p-hydroxypropiophenone, m-hydroxypropiophenone, o-hydroxypropiophenone, p-hydroxybutyrophenone, m-hydroxybutyrophenone, o-hydroxybutyrophenone, p-hydroxyisobutyrate, m-hydroxyisobutyrate, o-hydroxyisobutyrate, 2-acetylbiphenyl, 3-acetylphenyl, 4-acetylbiphenyl, 2-propenylboronic, 3-propenylboronic, 4-propenylboronic, p-phenylbutyrate, m-phenylbutyrate, o-phenylbutyrate, p-phenylazopyridine, m-phenylazopyridine, o-phenylsalicylate, p-methylacetophenone, m-methylacetophenone, o-methylacetophenone, p-methylpropiophenone, m-methylpropiophenone, o-methylpropiophenone, p-methylbutyrate, m-methylbutyrate, o-methylbutyrate, p-methylisobutylketone, m-methylisobutylketone, o-methylisobutylketone, p-ethylacetophenone, m-ethylacetophenone, o-ethylacetophenone, p-ethylpropylamine, m-ethylpropylamine, o-ethylpropylamine, p-ethylbutyrate, m-ethylbutyrate, o-ethylbutyrate, p-utilisabilito, m-utilisabilito, o-utilisabilito, p-propylacetophenone, m-propylacetophenone, o-propylacetophenone, 4-n-butylacetophenone, 4-isobutylacetophenone, 4-tertbutylphenol, 4-acetylacetone, 4-propionylacetate and 4-activate propiophenone etc.

From the above-mentioned aromatic ketones, from the viewpoint of reactivity and use, it is preferable to hydroxyacetophenone or hydroxypropiophenone. In particular, from the viewpoint of the reaction rate, are the preferred p-hydroxyacetophenone and m-hydroxyacetophenone with attached hydroxyl group instead of the p-methylacetophenone with attached methyl group and 4-acetylbiphenyl with the adjacent phenyl group.

Catalyst

The catalyst for use in the present invention contains from 0.1 to 20 wt%. atoms of ruthenium to the carrier.

The catalyst for use in the present invention, in which the number of deposited atoms of ruthenium is from 0.1 to 20 wt. -%, is not specifically defined in the method of obtaining. For example, the catalyst may be prepared by the method of application containing atoms of ruthenium compound on a carrier by the method of impregnation, drying method, deposition method and the like, and then the processing of his recovery, for example, by reduction with hydrogen or a chemical recovery with sodium borohydride, hydrazine, formic acid or the like, or without treatment restoring obtaining the desired catalyst.

If it contains an atom of ruthenium compound includes, for example, Ki is the Rath of ruthenium chloride, hydrate ruthenium bromide, hydrate of oxide of ruthenium chloride examinatione, bromide examinatione, declarationstatementast, triacetone ruthenium, tributenetherlands etc.

The medium may be any medium that is inert with respect to the substituents of the aromatic compound that is a starting material for hydrogenation under the reaction conditions, and may be organic or inorganic carrier, including, for example, activated carbon, ion exchange resin, silica, α-alumina, γ-alumina, silica-alumina, zeolite, and various types of metal oxides, composite oxides, etc. are Particularly preferable, from the viewpoint of selectivity are aluminum oxide and activated carbon.

The amount of ruthenium applied to a catalyst for use in the invention lies in the interval from 0.1 to 20 wt%. from the total mass of the catalyst. When the amount is less than 0.1 wt. -%, a very large number of catalyst must be used to achieve a satisfactory degree of hydrogenation of the nucleus, and industrial use, it would be difficult. When the quantity is more than 20 wt. -%, the share of ruthenium, taken by then, it may unnecessarily increased, and, if so, may occur hydrogenolysis or restoration of the acyl groups in the pores, where the maps in the Oia insufficient, and in this regard may be reduced selectivity. From this point of view, the applied amount is preferably from 0.5 to 10 wt. -%, more preferably from 2 to 5% of the mass.

The amount of catalyst used in the present invention may vary depending on the amount deposited of the active ingredient, type gidrirovannogo starting material, the reaction conditions and the other, but usually the amount is preferably lies in the range from 0.05 to 0.5 in terms of relationship to the mass of the original material (1). From a technological point of view is more preferable amount is in the range from 0.1 to 0.3.

Hydrogenation

According to the method of receiving according to the invention is a saturated aliphatic ketone is produced by hydrogenation of the nucleus of the aforementioned aromatic ketone represented by the General formula (1), the hydrogen pressure in the presence of a solvent at a temperature of from 20 to 120°C.

Hydrogenation in the present invention can be achieved in the absence of solvent depending on the type gidrirovannogo the starting material and reaction conditions, however, the hydrogenation is preferably carried out in a solvent, based on the fact that the selectivity can be increased by the choice of solvent, the most suitable for the intended reaction, and that reaction time can be shortened.

Not bouchiemarajuana specifically, the solvent for use in this invention may be a connection, there is little active in hydrogenation and can dissolve the starting material. As specific examples may be mentioned hydrocarbons that do not have double bonds, such as n-pentane, n-hexane, cyclohexane; ethers, such as diethyl ether, disutility ether, tetrahydrofuran; alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, 2-butanol, tert-butanol, n-hexanol, cyclohexanol; calogeropoulou, such as carbon tetrachloride, dichloromethane, trichloroethane.

In the present invention among the above-mentioned preferred solvents are saturated aliphatic alcohols having from 2 to 5 carbon atoms, a linear or branched ethers or aliphatic hydrocarbon having 5 to 10 carbon atoms from the point of view of the absence of side reactions and ease of handling during production.

The above solvents may be used singly or may be used in combination of two or more of them.

More preferred are diethyl ether, tetrahydrofuran, methanol, ethanol, n-propanol, cyclohexanol, n-hexane, heptane, and even more preferred is tetrahydrofuran.

Without being specific is definitely, the ratio of solvent to be used in the calculation of its mass, is preferably in the range from 0.05 to 100, more preferably from 0.1 to 20 in terms of mass relation relative to the source material (1).

The hydrogen used in the reaction may be any of hydrogen, typically used in the industry, however, when using hydrogen, in which the amount of impurity carbon monoxide is small, the catalyst activity can be excellent. Accordingly, the content of carbon monoxide in the hydrogen is preferably at most 1%.

While not specifically defined, the hydrogen pressure during the reaction may be any high pressure, however, if the pressure is too low, the reaction may take longer than you want, and if the pressure is too high, the rate of consumption of hydrogen can be increased. Accordingly, the pressure preferably lies in the range from 0.5 to 20 MPa, more preferably in the range from 1 to 10 MPa.

The temperature during the reaction can vary greatly depending on the type gidrirovannogo starting material, the reaction conditions and reaction time, and can be appropriately determined in the range from 0 to 200°C, but preferably lies in the range from 20 to 120°C. from the viewpoint of selectivity and economic the x reasons. In particular, for the source material having substituents with high reactivity, selectivity may be increased when the temperature is chosen preferably in the range from 20 to 100°C., more preferably from 30 to 80°C., even more preferably from 30 to 60°C.

The reaction time may be a time during which completes the absorption of hydrogen. Time may vary depending on the type gidrirovannogo source material, amount of catalyst and other reaction conditions and therefore cannot be determined without scatter. Typically, the time may be from 0.5 to 20 hours.

As described above, the hydrogenation of the nucleus substituted aromatic ketone easy network planned hydrogenated product with high selectivity.

More precisely, the advantage of this method is that the hydrogenation kernel provides very high selectivity.

In addition, the above-mentioned ruthenium catalyst available at very inexpensive prices. Further, the catalyst can be reused, and therefore, the method of hydrogenation of the kernel method is additionally advantageous from the viewpoint of cost reduction on the catalyst.

The equipment for carrying out the reaction, not specifically described, may be any hardware that is resistant to the desired hydrogen pressure.

By way of carrying out the reaction, preferred is entrusted is a periodic way from the point of view, what used catalyst has to be separated in the liquid phase at the reaction temperature.

For example, the raw material of the aromatic ketone, the ruthenium catalyst and the solvent serves in an autoclave equipped with an electromagnetic stirrer, and then the contents of the mix and set the temperature of the liquid, then the pressure is increased to 0.5-20 MPa introduced into the reactor with hydrogen, then under conditions where the pressure and temperature of the liquid support such, impose additional hydrogen so as to maintain the pressure constant, then the autoclave stand itself up until hydrogen is no longer absorbed, after which the oil phase is selected by filtering or similar method and then analyzed by gas chromatography, determining that the formed cyclohexylacetate.

Cyclohexylethylamine

The present invention relates to a method for producing a saturated aliphatic ketone, which receive cyclohexylacetate represented by the above General formula (2). In the General formula (2), n indicates an integer from 1 to 3; R represents a hydroxyl group, tsiklogeksilnogo group, alkyl group having from 1 to 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms. R and n in the General formula (2) are the same as mentioned here above for the similar material - aromatic ketone.

Hydrogenated on the core product - cyclohexylacetate, which is obtained according to the present invention, can be the target product having a high purity, even if the catalyst is removed by filtration or the like method, and then simply removed one solvent, however, the product may be further purified according to a conventional known method of distillation, crystallization, etc. of the Catalyst recovered by this time, can be reused in the reaction.

Selectivity for cycloalkylation obtained according to the production method of the present invention, is higher than in conventional methods, and is usually at least 50%, more preferably at least 85%, even more preferably at least 90%, and even more preferably at least 95%.

The output of cyclohexylethylamine can usually be at least 50%, but is preferably at least 60%, more preferably at least 85%, even more preferably at least 90%, and even more preferably at least 95%.

The present invention will be described more specifically below, but the present invention is not limited to the examples.

Conditions of gas chromatography analysis

The results of the reaction was estimated by gas chromatography. For gas HRO is ecografia used instrument GC-17A, available from Shimadzu Corporation with capillary column HR-1 (⌀ 0.32 mm × 25 m), available from Shinwa Chemical Industries Ltd. With regard to the conditions of heating, the system was heated from 100°C to 320°C at 5°C/min, the Ratio of CIS/TRANS isomer of cyclohexane ring were determined using a capillary column Xylene Master (⌀ 0.32 mm × 50 m), available from Shinwa Chemical Industries Ltd. With regard to the conditions of heating, the system was heated from 70°C to 120°C at a rate of 2°C/min

Example 1

Chemical formula (4)

2 g of catalyst 5% Ru/alumina, available from N.E. CHEMIKAT, 10 g of p-hydroxypropiophenone (chemical reagent available from Wako Pure Chemicals) and 100 ml of tetrahydrofuran (chemical reagent available from Wako Pure Chemicals) was introduced into a 200 ml autoclave, gas in the reactor blew gaseous nitrogen, the reactor was adjusted at 50°C and then it was added hydrogen so that the pressure in the reactor could be equal to 4 MPa, and continued the reaction for 5 hours, after which the flow of hydrogen was stopped. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 98%, and the yield was 98%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 64/36.

Example 2

Hider is the study and treatment of the reaction liquid was performed in the same way, as in example 1, except that the solvent was ethanol (chemical reagent available from Wako Pure Chemicals). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 64/36.

Example 3

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that the solvent was methanol (chemical reagent available from Wako Pure Chemicals). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 66/34.

Example 4

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that the solvent was n-butanol (chemical reagent available from Wako Pure Chemicals). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material with which accounted for 100%, the selectivity for 4-propionyloxy was 89%, and the yield was 89%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 64/36.

Example 5

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that here again used catalyst used in example 1. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 93%, and the yield was 93%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 66/34.

Example 6

70 g of a catalyst of 5% Ru/alumina, available from N.E. CHEMIKAT, 350 g of p-hydroxypropiophenone and 1750 ml of ethanol were introduced into a 10-liter autoclave, gas in the reactor blew gaseous nitrogen, the reactor was adjusted at 50°C and then it was added hydrogen so that the pressure in the reactor could be equal to 4 MPa, and continued the reaction for 10 hours, after which the flow of hydrogen was stopped. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 93%, and the yield was 93%. Aspect] is a solution of CIS/TRANS - isomers of the cyclohexane ring was 64/36.

Example 7

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 5% Ru/carbon (hydrate) type a, available from N.E. CHEMIKAT, and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 54%, and the yield was 54%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 69/31.

Example 8

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 5% Ru/carbon (hydrate) type, available from N.E. CHEMIKAT, and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 90%, and the yield was 90%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 64/36.

Example 9

Hydrogenation and processing reactionneuropathy conducted in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 5% Ru/carbon (hydrate) type K available from N.E. CHEMIKAT, and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 60%, and the yield was 60%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 67/33.

Example 10

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 5% Ru/carbon (hydrate) type R available from N.E. CHEMIKAT, and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 90%, and the yield was 90%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 68/32.

Example 11

Chemical formula (5)

Hydrogenation and treatment of the reaction liquid was performed the same about what atom, as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used p-hydroxyacetophenone (chemical reagent available from Wako Pure Chemicals), and the reaction time was 4 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-acetylcyclohexanone was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 64/36.

Example 12

Chemical formula (6)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used m-hydroxyacetophenone (chemical reagent available from Wako Pure Chemicals), and the reaction time was 5 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 3-acetylcyclohexanone was 97%, and the yield was 97%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 40/60.

Example 13

Chemical formula (7)

Gadirov the s and the treatment of the reaction liquid was performed in the same way, as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used on hydroxyacetophenone (chemical reagent available from Wako Pure Chemicals), and the reaction time was 5 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 2-acetylcyclohexanone was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 60/40.

Example 14

Chemical formula (8)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2, used 4-propionyl 1,1'-biphenyl (chemical reagent, available from Tokyo Chemical Industry), and the reaction time was 11 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyl 1,1'-bicyclohexyl was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 72/28.

Example 15

Hydrogenation and treatment of the reaction liquid held still the same way as in example 14, except that the solvent was hexane (chemical reagent available from Wako Pure Chemicals). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyl 1,1'-bicyclohexyl was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 72/28.

Example 16

Chemical formula (9)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used 1,4-diacetylbenzene (chemical reagent, available from Tokyo Chemical Industry). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 1,4-deacetyltaxol was 97%, and the yield was 97%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 76/24.

Example 17

Chemical formula (10)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropionate is she, used in example 2 was used 4'-methylacetophenone (chemical reagent available from Wako Pure Chemicals), and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 1-acetyl-4-methylcyclohexane was 96%and the yield was 96%. The ratio of CIS/TRANS isomers of the cyclohexane ring was 22/78.

Comparative example 1

Chemical formula (11)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used acetophenone, and the reaction time was 6 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100% and selectivity for ethylcyclohexane was 99%.

Comparative example 2

Chemical formula (12)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used 4'-forceto the northward (chemical reagent, available from Wako Pure Chemicals), and the reaction time was 3.5 hours. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for ethylcyclohexane was 74% and the selectivity for 1-ethyl-4-forcelogix was 26%.

Comparative example 3

Chemical formula (13)

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 2, except that instead of p-hydroxypropiophenone used in example 2 was used p-aminoacetophenone (chemical reagent available from Wako Pure Chemicals). After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 58%, and the reaction liquid was liquid mixture of 4-amino-1-vinylbenzene (selectivity 22%), 1-(4-aminocyclohexane)ethanol selectivity 27%) and 1-(4-AMINOPHENYL)ethanol (selectivity 41%).

Comparative example 4

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used a copper-chromium catalyst (203s vehicles), available from JGS Catalysts and hemicals, the reaction time was 3 hours and the reaction temperature was 140°C. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 0%, and the selectivity for 4-propileno was 100%.

Comparative example 5

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 2% Ru/carbon (hydrate), available from N.E. CHEMIKAT, the reaction time was 2 hours and the reaction temperature was 140°C. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 0%, and the selectivity for 4-propylcyclohexanone was 93%. The ratio of CIS/TRANS isomers of the cyclohexane ring at the 4-propylcyclohexanone was 53/47.

Comparative example 6

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 1, except that instead of the catalyst 5% Ru/alumina used in example 1 was used, the catalyst 5% Ru/carbon (hydrate), t is p STD, available from N.E. CHEMIKAT, the reaction temperature was 140°C, and the solvent was cyclohexane. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 0%, and the selectivity for 4-propylcyclohexanone was 95%. The ratio of CIS/TRANS isomers of the cyclohexane ring at the 4-propylcyclohexanone was 55/45.

Comparative example 7

Hydrogenation and treatment of the reaction liquid was performed in the same manner as in example 7, except that the reaction temperature was 140°C. After the reaction, the catalyst was removed by filtration and the resulting filtrate was analyzed by gas chromatography. It was confirmed that the conversion of the raw material was 100%, the selectivity for 4-propionyloxy was 14%, and the selectivity for 4-propylcyclohexanone was 82%.

Industrial applicability

Cyclohexylethylamine obtained in the present invention, used as raw materials for paints, fragrances, pharmaceuticals, agrochemical means of functional materials for electronics and optical functional materials.

1. A method of obtaining a saturated aliphatic ketone, in which the aromatic ketone represented about is her formula (1):
[chemical formula (1)]

(where in the chemical formula (1) n indicates an integer from 1 to 3; R represents a hydroxyl group, phenyl group, alkyl group having from 1 to 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms),
hydronaut the core of hydrogen under pressure in the presence of a solvent at a temperature of from 20 to 120°C and in the presence of a catalyst, which is from 0.1 to 20 wt%. atom of ruthenium on a carrier and thereby gain cyclohexylacetate represented by the General formula (2):
[chemical formula (2)]

(where in the chemical formula (2), n indicates an integer from 1 to 3; R represents a hydroxyl group, tsiklogeksilnogo group, alkyl group having from 1 to 4 carbon atoms, or acyl group having from 1 to 4 carbon atoms).

2. A method of obtaining a saturated aliphatic ketone according to claim 1, in which the carrier is alumina or activated carbon.

3. A method of obtaining a saturated aliphatic ketone according to claim 2, in which the carrier is alumina.

4. A method of obtaining a saturated aliphatic ketone according to any one of claims 1 to 3, in which the aromatic ketone represented by the General formula (1)is p-hydroxyacetophenone or hydroxypropiophenone.

5. The way the floor is placed a saturated aliphatic ketone according to any one of claims 1 to 3, in which the solvent is a saturated aliphatic alcohol having from 2 to 5 carbon atoms, linear or cyclic simple ether, or a saturated aliphatic hydrocarbon having 5 to 10 carbon atoms.

6. A method of obtaining a saturated aliphatic ketone according to any one of claims 1 to 3, in which the hydrogen pressure is from 0.5 to 20 MPa.



 

Same patents:

The invention relates to 4-substituted anthracyclinone used as intermediate compounds and derived from them anthracyclinebased

FIELD: chemistry.

SUBSTANCE: invention relates to chemical derivatives of adamantane and specifically to a novel method of producing 2-(2-alkyl(dialkyl)amino)adamantyl-alkyl(aryl)ketones of general formula R=-NHCH3: R1=Et,-CH2-CH=CH2; : R1=Me, Et,-CH2-CH=CH2, Ph,-CH2Ph; : R1= Me, Etwhich can be used as intermediate products in synthesis of certain biologically active substances. The novel method involves reacting 2-alkylamino(dialkylamino)-2-cyanoadamantanes from the group: 2-methylamino-2-cyanoadamantane, 2-N-piperidino-2-cyanoadamantane, 2-N-morpholino-2-cyanoadamantane with Grignard reagents from the group: methylmagnesium iodide, ethylmagnesium bromide, allylmagnesium chloride, phenylmagnesiuim bromide, benzylmagnesium chloride in a medium of dry diethyl ether or a tetrahydrofuran-ether mixture in molar ratio of reagents equal to 1:2-2.03, respectively, at temperature 30-45°C for 4-5 hours.

EFFECT: wider range of adamantane derivatives, design of a method for synthesis of novel adamantane derivatives with high output.

9 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of cyclic alkane oxidation by oxidation agent for obtaining a product, where oxidation is performed in cracking fractionator including vat zone at bottom end, head zone at top end, and reaction zone between vat and head zones. Reaction mix is kept boiling in reaction zone, and oxidation agent is added into reaction zone in at least two split flows. Non-reacted raw material leaving reaction zone is recycled into reaction zone. Gas containing molecular oxygen is used as oxidation agent, and reaction mix containing target product is collected below reaction zone.

EFFECT: simple and cost-effective method of obtaining the product, enhanced conversion of source material and selectivity of target product generation.

6 cl, 1 dwg, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of cyclohexanol or cyclohexanone via hydrogenation of phenol or benzene with hydrogen in presence of catalyst and diluent followed by hydration in case of using benzene as starting material. Process is characterized by that hydrogen and benzene or hydrogen and phenol preheated in heat exchanger, provided with condensate intake control circuit, and circulation gas are supplied to vaporizer and preheater, provided with heating steam consumption control circuits, through supply lines provided with shutoff valves. Phenol or benzene and circulation gas, as well as heating steam and condensate consumptions are specified and adjusted. Preheated mix is then fed into separator to separate gas from liquid phase, which is removed, while remaining gas mixture is sent to hydrogenation reactors comprising temperature control zones and heat-extracting tube-type condensers and provided with phenol or benzene, hydrogen and condensate control circuits, temperature sensors connected to controllers to adjust consumptions of phenol or benzene, hydrogen and condensate, and wherein diluent volume level compared to that of catalyst is controlled and hydration temperature is measured. Resulting product enters cooler and then separation column provided with cyclohexanol or cyclohexanone recovery level control and adjusting, wherefrom it is directed to gas circulation line comprising cooler, separator, and compressor equipped with pipelines with circulation gas consumption control circuits.

EFFECT: increased productivity with regard to cyclohexanol or cyclohexanone.

2 dwg

The invention relates to an improved method of decomposition of the hydroperoxide with the formation of a mixture containing the corresponding alcohol and ketone, comprising the stage of: a) adding water in the amount of 0.5-20% in the mixture containing the hydroperoxide; (b) the deletion of specified volume of water in such a way that together with water removes water-soluble impurities; C) removing the remaining water in such a way that the reaction mixture is not more than 2% of water; and (d) decomposition of the specified hydroperoxide by contacting the reaction mixture with a catalytic amount of a heterogeneous catalyst containing gold, supported on a carrier

FIELD: chemistry.

SUBSTANCE: method involves Wittig olefination of the 6E-isomer of 2E-2,6-dimethyl-8-triphenylsilyloxyocta-2,6-dien-4-yn-1-al (synthon C10)ylid, generated in situ from β-cyclogeranyltriphenyl phosphonium halide, removal of triphenylsilyl protection in the obtained silylated 13E-isomer of 11,12-didehydroretinol. After removal triphenylsilyl protection, the obtained 13E-isomer of 11,12-didehydroretinol is oxidised to 11,12-didehydroaldehyde using MnO2 without extracting the semi-product separately and further purification procedures, and stereo-specific reduction of the triple bond in 11,12-didehydroaldehyde is then carried out in via hydrogenation on a Lindlar catalyst to obtain the desired 11-cis-retinal isomer, where generation of ylide from β-cyclogeranyltriphenyl phosphonium halide is carried out under the following conditions: a) NaH in tetrahydrofuran at 0-5°C, b) anhydrous K2CO3 in dichloromethane, in the presence of interphase transfer catalysts - quaternary ammonium salts at 20-25°C, or c) 1,2-epoxybutane in dichloromethane at 50-60°C.

EFFECT: obtaining medicinal agents for preventing or therapy of severe pathologies of the human optical system.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: organic chemistry, chemical chemistry.

SUBSTANCE: invention relates to a method for synthesis of compound of the formula (I): . Method involves interaction of compound of the formula (II)

with compound of the formula (III) in the presence of a catalyst chosen from cationic complexes of bivalent ruthenium and polar organic solvent. Also, invention relates to a novel compound of the formula (I) that is used in synthesis of phyton and vitamin E, and to a method for synthesis of phyton also.

EFFECT: improved method of synthesis.

20 cl, 3 ex

The invention relates to a method for producing 4,4-dimethyl-1-(p-chlorophenyl)pentane-3-one, which is an intermediate product to obtain pesticides and pharmaceutical products, including tebuconazole

FIELD: organic chemistry, chemical chemistry.

SUBSTANCE: invention relates to a method for synthesis of compound of the formula (I): . Method involves interaction of compound of the formula (II)

with compound of the formula (III) in the presence of a catalyst chosen from cationic complexes of bivalent ruthenium and polar organic solvent. Also, invention relates to a novel compound of the formula (I) that is used in synthesis of phyton and vitamin E, and to a method for synthesis of phyton also.

EFFECT: improved method of synthesis.

20 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves Wittig olefination of the 6E-isomer of 2E-2,6-dimethyl-8-triphenylsilyloxyocta-2,6-dien-4-yn-1-al (synthon C10)ylid, generated in situ from β-cyclogeranyltriphenyl phosphonium halide, removal of triphenylsilyl protection in the obtained silylated 13E-isomer of 11,12-didehydroretinol. After removal triphenylsilyl protection, the obtained 13E-isomer of 11,12-didehydroretinol is oxidised to 11,12-didehydroaldehyde using MnO2 without extracting the semi-product separately and further purification procedures, and stereo-specific reduction of the triple bond in 11,12-didehydroaldehyde is then carried out in via hydrogenation on a Lindlar catalyst to obtain the desired 11-cis-retinal isomer, where generation of ylide from β-cyclogeranyltriphenyl phosphonium halide is carried out under the following conditions: a) NaH in tetrahydrofuran at 0-5°C, b) anhydrous K2CO3 in dichloromethane, in the presence of interphase transfer catalysts - quaternary ammonium salts at 20-25°C, or c) 1,2-epoxybutane in dichloromethane at 50-60°C.

EFFECT: obtaining medicinal agents for preventing or therapy of severe pathologies of the human optical system.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining saturated aliphatic ketone, represented by the general formula (2), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a cyclohexyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), applied as an initial material for the production of medications, agrochemical preparations, optic functional materials and functional materials for electronics. The method consists in hydrogenation of a nucleus of an aromatic ketone, represented by the general formula (1), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a phenyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), with hydrogen under pressure in the presence of a solvent at a temperature from 20 to 120°C and in the presence of a catalyst, which carries from 0.1 to 20 wt % of the ruthenium atom on a carrier.

EFFECT: method makes it possible to obtain the target product with high selectivity.

6 cl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrogenating α,β-unsaturated ketones of general formula , where R1, R2=H or R1-R2=-(CH2)3-, which includes hydrogenating benzal alkanone with hydrogen gas in a solvent medium in the presence of a catalyst. The benzal alkanone used is benzalacetone or benzalcyclohexanone, and the catalyst used is colloidal nickel particles obtained by reducing nickel (II) chloride with lithium aluminium hydride, and the process is carried out at atmospheric pressure of hydrogen in a tetrahydrofuran medium at 55-60°C.

EFFECT: invention enables to obtain saturated ketones with high output using a simple method.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hexahydro-iso-alpha-acids from iso-alpha-acids (or tetrahydro-iso-alpha-acids), which includes mixing iso-alpha-acids (or tetrahydro-iso-alpha-acids) with a heterogeneous ruthenium-containing catalyst, which catalyses hydrogenation of iso-alpha-acids or tetrahydro-iso-alpha-acids to obtain hexahydro-iso-alpha-acids, in the absence of a solvent or in the presence of a solvent phase (e.g., carbon dioxide, water, ethanol or other organic solvent or mixtures thereof) and in the absence or in the presence of other hop compounds (such as beta-acids). The obtained mixture is then exposed to a temperature at which the reaction medium, which contains an iso-alpha-acid (or tetrahydro-iso-alpha-acid), has a sufficiently low viscosity to be easily mixed with the heterogeneous ruthenium-containing catalyst, and held in an atmosphere containing hydrogen over a reaction time sufficient for efficient conversion of the reactant, which is an iso-alpha-acid (or tetrahydro-iso-alpha-acid), into a hexahydro-iso-alpha-acid.

EFFECT: methods enable to obtain end products with high selectivity and without using an extra reduction step using an inorganic reducing agent.

21 cl, 2 dwg, 10 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing saturated aldehydes by contacting a liquid organic feed containing unsaturated aldehydes with hydrogen or hydrogen-containing gas in presence of crustal catalyst comprising palladium particles of not more than 6 nm in size, applied in form of a layer not thicker than 150 microns on exterior surface of porous alumina carrier granules. Herewith the carrier has not less than 60% of pores with a diameter of 5 to 50 nm, and the hydrogenation is carried out at a liquid feed rate of 1-4 h-1.

EFFECT: producing target products with high selectivity at high process efficiency and feedstock conversion.

25 cl, 8 dwg, 6 tbl, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to production of cyclohexanol or cyclohexanone via hydrogenation of phenol or benzene with hydrogen in presence of catalyst and diluent followed by hydration in case of using benzene as starting material. Process is characterized by that hydrogen and benzene or hydrogen and phenol preheated in heat exchanger, provided with condensate intake control circuit, and circulation gas are supplied to vaporizer and preheater, provided with heating steam consumption control circuits, through supply lines provided with shutoff valves. Phenol or benzene and circulation gas, as well as heating steam and condensate consumptions are specified and adjusted. Preheated mix is then fed into separator to separate gas from liquid phase, which is removed, while remaining gas mixture is sent to hydrogenation reactors comprising temperature control zones and heat-extracting tube-type condensers and provided with phenol or benzene, hydrogen and condensate control circuits, temperature sensors connected to controllers to adjust consumptions of phenol or benzene, hydrogen and condensate, and wherein diluent volume level compared to that of catalyst is controlled and hydration temperature is measured. Resulting product enters cooler and then separation column provided with cyclohexanol or cyclohexanone recovery level control and adjusting, wherefrom it is directed to gas circulation line comprising cooler, separator, and compressor equipped with pipelines with circulation gas consumption control circuits.

EFFECT: increased productivity with regard to cyclohexanol or cyclohexanone.

2 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns method of cyclic alkane oxidation by oxidation agent for obtaining a product, where oxidation is performed in cracking fractionator including vat zone at bottom end, head zone at top end, and reaction zone between vat and head zones. Reaction mix is kept boiling in reaction zone, and oxidation agent is added into reaction zone in at least two split flows. Non-reacted raw material leaving reaction zone is recycled into reaction zone. Gas containing molecular oxygen is used as oxidation agent, and reaction mix containing target product is collected below reaction zone.

EFFECT: simple and cost-effective method of obtaining the product, enhanced conversion of source material and selectivity of target product generation.

6 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining saturated aliphatic ketone, represented by the general formula (2), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a cyclohexyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), applied as an initial material for the production of medications, agrochemical preparations, optic functional materials and functional materials for electronics. The method consists in hydrogenation of a nucleus of an aromatic ketone, represented by the general formula (1), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a phenyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), with hydrogen under pressure in the presence of a solvent at a temperature from 20 to 120°C and in the presence of a catalyst, which carries from 0.1 to 20 wt % of the ruthenium atom on a carrier.

EFFECT: method makes it possible to obtain the target product with high selectivity.

6 cl, 24 ex

FIELD: chemistry.

SUBSTANCE: method includes depositing an active component - copper - from an aqueous solution of an ammonia-carbonate complex on an oxide solid support, heat treatment and granulation. Deposition of the active component is carried out on an oxide solid support consisting of a mixture of white soot and boehmite in weight ratio of (2.5-3.5):1, and granulation of the catalyst paste is carried out by extrusion.

EFFECT: method enables to obtain a catalyst with high thermal stability while maintaining high selectivity and activity.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method involves the preparation of cyclohexanone by cyclohexene oxidation, the isolation of cyclohexanone from a mixture of water-acetonitrile-cyclohexene-cyclohexanone of any composition by combining in the process scheme an autoclaving rectification with a medium-volatile separation agent acetonitrile and three-phase delamination in a Florentine vessel followed by feeding each layer to the rectification columns. The process scheme preferably comprises four distillation columns and a Florentine vessel.

EFFECT: separation of a reaction mixture of any composition into practically pure components that meet the quality requirements of marketable products.

2 cl, 2 dwg, 4 ex

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