Method of producing 2,6-dimethyl-1-naphthaldehyde

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 2,6-dimethyl-1-naphthaldehyde which is used in industrial chemical materials and raw materials for pharmaceutical products, pesticides, optical functional materials and electronic functional materials. The method involves formylation of 2,6-dimethylnaphthalene with carbon monoxide in the presence of hydrogen fluoride in terms of moles in amount ranging from 5- to 100-fold and boron trifluoride in terms of moles in amount ranging from 0.5- to 3.5-fold compared to the amount of 2,6-dimethylnaphthalene, and at reaction temperature ranging from 35 to 70C.

EFFECT: method enables to obtain and end product with high selectivity.

15 ex

 

The technical field

The present invention relates to a method for producing 2,6-dimethyl-1-naphthaldehyde, which is suitable for use in industrial chemical materials and supplies of raw materials for pharmaceutical products, pesticides, optical functional materials, electronic functional materials and the like.

The level of technology

To date naphthaldehyde in General synthesized by known methods. Examples of such methods include a method of obtaining 7-methyl-1-naphthaldehyde, comprising carrying out the reaction between 2,7-dimethylnaphthalene and halogenation reagent to obtain monohalogenated substances and oxidation of the obtained 7-methyl-2-halogenerator (see patent document 1); a method for aromatic aldehydes, comprising carrying out the reaction between aromatic halogenation compound and nitric acid in the presence of a surfactant (see patent document 2); a method of producing dimethylnaphthalene, including the addition of aluminium chloride to a mixture containing hydrogen chloride, cyanide of zinc and dimethylnaphthalene (see non-patent document 1); and the method of production, including the transformation of alkylnaphthalene in alkylnaphthalene in the presence of hydrogen cyanide and aluminum chloride is based (see non-patent document 2). Another known method of obtaining diallylmethylamine from dialkylphenol includes carrying out the reaction between dialkylphenols and carbon monoxide in the presence of a catalyst derived from hydrogen fluoride and boron TRIFLUORIDE (see patent document 3).

Patent document 1: Japanese laid patent application (kokaiNo. 08-268990.

Patent document 2: Japanese laid patent application (kokaiNo. 50-117737.

Patent document 3: U.S. patent No. 4460794.

Non-patent document 1: F. M. Aslam and P. H. Gore, J. Chem. Soc., Perkin Trans. I, 1972, p. 892 and 893.

Non-patent document 2: L. E. Hinkel, E. E. Ayling, and J. H. Beynon, J. Chem. Soc., 1936, p. 339 and 342.

The problem addressed by the invention

In the method described in patent document 1, it is preferable to use a halogenation reagent such as N-bromosuccinimide. However, this expensive reagent, as N-bromosuccinimide, is disadvantageous from a cost perspective. In addition, the use of amine at the stage of oxidation creates a serious burden for the environment, and this method is not suitable for large-scale production. Although the methods described in patent documents 1 and 2, essentially include the conversion of a methyl group to a formyl group, so far not been described for any l is Bo way, on which the formyl group was introduced in position on the aromatic ring, with which a methyl group is not connected, while maintaining the aromatic ring methyl group.

In the methods described in non-patent documents 1 and 2, use cyanide compound, which creates a serious burden for the environment. Therefore, these methods are difficult for the actual implementation on an industrial scale and are characterized by low activity in the reaction and performance that is a problem.

The method described in patent document 3, is a promising candidate as a method for industrial production, since the used catalyst can be easily sent to recycling. Thus, the inventors of the present invention under the conditions described in patent document 3, previously tried to introduce formyl groups in 2,6-dimethylnaphthalene acting as material feedstock. As a result, in addition to 2,6-dimethyl-1-naphthaldehyde used as an optical functional material, in the form of by-product received almost equivalent to the amount of 3,7-dimethyl-1-naphthaldehyde. Due to almost identical boiling points for these two isomers isomers are difficult to separate from each other even when the performance of the mixture distillation. A possible approach to the separation of the isomers is rectification when a large number of stages. However, this approach is economically unviable, unless found effective utilization of by-product 3,7-DMAL. In the case of 2,6-dimethyl-1-naphthaldehyde as an optical functional material levels of 3,7-dimethyl-1-naphthaldehyde it reduced to 30% (mol.) and less. There is therefore a need for a reliable way to obtain 2,6-dimethyl-1-naphthaldehyde with high selectivity.

Resolving problems

Given the above, the inventors of the present invention conducted extensive research aimed at finding a reliable highly selective method of producing 2,6-dimethyl-1-naphthaldehyde of 2,6-dimethylnaphthalene and carbon monoxide in the presence of a catalyst derived from hydrogen fluoride and boron TRIFLUORIDE, and found that the ratio between the amount of 3,7-dimethyl-1-naphthaldehyde and the total amount of 2,6-dimethyl-1-naphthaldehyde and 3,7-dimethyl-1-naphthaldehyde determined during formirovaniya and does not change during the distillation for cleaning or other processes. The inventors have also found that this ratio can steadily be suppressed to a level equal to 30% (mol.) or less, d is the query result is the proper choice of conditions formirovaniya. The present invention was made on the basis of these discoveries.

Accordingly the present invention provides a method of obtaining 2,6-dimethyl-1-naphthaldehyde result formirovaniya 2,6-dimethylnaphthalene under the action of carbon monoxide, characterized in that formirovanie carried out in the presence of hydrogen fluoride in calculating the moles in a quantity ranging from 5 - to 100-fold and boron TRIFLUORIDE in calculating the moles in amounts in the range from 0.5 to 3.5-fold in comparison with the amount of 2,6-dimethylnaphthalene and at the reaction temperature in the range from 35 to 70C.

Effects of invention

In accordance with the method of the present invention is advantageous from an industrial point of view can be obtained 2,6-dimethyl-1-naphthaldehyde, which is suitable for use in industrial chemical materials and supplies of raw materials for pharmaceutical products, pesticides, optical functional materials and electronic functional materials, when the ratio between the amount of 3,7-dimethyl-1-naphthaldehyde and the total amount of 2,6-dimethyl-1-naphthaldehyde and 3,7-dimethyl-1-naphthaldehyde equal to 30% (mol.) or less.

The best way of carrying out the invention

In the present invention 2,6-dimethylnaphthalene (here and in the remainder of this paper is on is designated as 2,6-DMN, and the 2,7 isomer-dimethylnaphthalene known as 2,7-DMN), acting as material feedstock, is a well-known white compound with a melting point of 111C. and the boiling temperature of 262C (at ambient pressure). On the way to obtain 2,6-DMN any special restrictions are not imposed, and can be used a method of obtaining. In one method of obtaining 2,6-DMN coal tar, petroleum distillates, and the like appropriately diluted with toluene or similar solvent, followed by sufficient cooling to obtain, thereby - 2,6-DMN and 2.7-DMN. Two dedicated substances dissolved in a solvent such as m-xylene, and the solution perepuskat through the adsorbent, thereby selectively receiving high-purity 2,6-DMN (see, for example, Japanese patent publicationKohyoNo. 2001-527054). In another way naphthalene or methylnaphthalene are transalkylation and isomerization in the presence of zeolite catalyst and using polymethylpentene, and from the reaction mixture allocate 2,6-DMN as a result of, for example, distillation (see, for example, Japanese laid patent application (kokaiNo. 6-040958). In still one other way 1,5-dimethylnaphthalene obtained from o-xylene and butadiene, will isomerized in the presence of a catalyst such as hydrogen fluoride and isomerized product is mixed with an aliphatic or alicyclic saturated hydrocarbon, followed by crystallization for separation, thus, 2,6-DMN (see, for example, Japanese laid patent application (kokaiNo. 9-291045).

Corresponding to the present invention a method of formirovaniya 2,6-DMN under the action of carbon monoxide implement in the presence of a catalyst derived from hydrogen fluoride (hereafter in this document referred to as HF) and boron TRIFLUORIDE (hereafter in this document referred to as BF3) (hereinafter in this document, the catalyst may be designated as catalyst HFBF3). Since HF and BF3acting as a component of a catalyst, characterized by high volatility, these components in the present invention upon completion of the reaction can be extracted and sent for recycling. Thus, recycling of the preparation of the catalyst of formirovaniya is not required, making the method cost-effective and reduces the load on the environment.

Carbon monoxide may contain an inert gas, such as nitrogen or methane. The partial pressure of carbon monoxide is preferably in the range from 0.5 to 5 MPa, more preferably from 1 to 3 MPa. This limitation of the range of partial pressure is preferred because of formirovanie will proceed sufficiently, and the reduction of the output of receipt, which otherwise is was would be caused by the passage of adverse reactions, such as isomerization and polymerization can be suppressed to a low level.

HF is preferably anhydrous. More specifically, the level of water content in HF is preferably 0.1% or less, more preferably 0.02% and less. HF in calculating the mole is used in a quantity ranging from 5 - to 100-fold in comparison with the amount of 2,6-DMN, preferably from 5 to 50 times, more preferably from 8 - to 50-fold, even more preferably from 10 to 50-fold, particularly preferably from 10 to 30-fold. If the amount of HF in calculating the moles, less than 5-fold in comparison with the amount of 2,6-DMN, decreases the percentage selectivity obtain 2,6-dimethyl-1-naphthaldehyde, while in the case of more than 100-fold, cannot be achieved, comparable to the size increases, which is economically disadvantageous.

BF3in calculating the moles used in amounts in the range from 0.5 to 3.5-fold in comparison with the amount of 2,6-DMN, preferably from 0.7 to 3 times, more preferably from 0.8 to 2-fold, even more preferably from 0.9 - to 1.2-fold. If the number BF3when per mole, less than 0.5-fold in comparison with the amount of 2,6-DMN, slows the passage of formirovaniya, and reduced interest shall electively obtain 2,6-dimethyl-1-naphthaldehyde, while in the case of amounts in excess of 3.5-fold, decreases the partial pressure of carbon monoxide in the gas phase, which consequently leads to lower output, that is not preferred.

Important factors to suppress the ratio between the amount of 3,7-dimethyl-1-naphthaldehyde (hereafter in this document referred to as 3,7-DMNL) and the total amount of 2,6-dimethyl-1-naphthaldehyde (hereafter in this document referred to as 2,6-DMNL) and 3.7-DMNL (hereafter in this document referred to as the 3.7 ratio) to 30% (mol.) and less are the aforementioned amount of HF and BF3in comparison with the amount of 2,6-DMN and the temperature at which conduct formirovanie.

In General, formirovanie in the presence of HF catalystBF3carried out at a temperature in the range from approximately 30to approximately 20C. However, in accordance with the method of the present invention, formirovanie carried out at a temperature in the range from 35 to 70C., preferably from 40 to 60C., more preferably from 45 to 55C. This temperature range cannot be specified on the basis of common sense experts in the relevant field of technology. In case of finding quantities of HF and BF3in comparison with the amount of 2,6-DMN within wisewoman is in range and controlled keeping the reaction temperature in the range from 35 to 70C possible with a high output will be to obtain 2,6-DMNL while possible steady suppression 3,7-ratio up to 30% (mol.) and less. If the reaction temperature less than 35C, 3,7-ratio will decrease, but significantly reduced the yield of the reaction. In addition, the quality of such products will be received large amounts of high-boiling compounds that make conducting formirovaniya on an industrial scale is difficult. In the case of a reaction temperature greater than 70C, will promotionals the formation of high-boiling compounds that will reduce the output.

The response time of any special restrictions are not imposed, and this time is preferably in the range from 1 to 10 hours, more preferably from 1 to 5 hours. In General, when choosing such a reaction time can be achieved sufficient interest, the degree of conversion of 2,6-DMN. At the end point of the reaction indicates the time when the absorption of carbon monoxide is terminated.

Formirovanie can be carried out in the absence or in the presence of a solvent. Any particular restrictions on the solvent does not impose as long as the solvent is capable of dissolving 2,6-DMN and will be inert with respect to 2,6-DMN, HF and BF3. Examples of the solvent include saturated aliphatic hydrocarbons such as hexane, heptane and decane. In the case of using a solvent, the amount of solvent in the calculation of the mass preferably is away in the range from 0.1 - to 10-fold in comparison with the amount of 2,6-DMN, more preferably from 0.5 to 3 times. The solvent additionally suppresses polymerization (adverse reaction), increasing the output of receipt. However, in the case of the use of large amounts of solvent will decrease the efficiency of the reaction, expressed in terms of volume, and to highlight the product, you will need the extra energy that are unfavorable for the plant.

Any special restrictions on the format of formirovaniya of the present invention does not impose as long as the resulting mixing of the gas phase and the liquid phase will be blended sufficiently. Can be used any way you choose from the periodic method, properities method, a continuous method and the like. Here and in the remainder of this document will describe the specific modes for periodic way, properities method and continuous method. However, the format formirovaniya this in any way is not particularly limited.

In a periodic manner in a reactor such as an autoclave, equipped with an electromagnetic stirrer, serves 2,6-DMN dissolved in the solvent, a predetermined amount of anhydrous HF and a predetermined number BF3. While stirring the contents of the liquid temperature kept in the range from 35 to 70C. the Pressure is s in the reactor increases, for example, to a value in the range from 0.5 to 3 MPa in the submission to him of carbon monoxide. Pressure support in the feed to the reactor of carbon monoxide, and the contents of the reactor is maintained at this temperature for one hour, the result can be obtained 2,6-DMAL. Obtaining 2,6-DMNL can be confirmed as a result of selection of the sample portion of the liquid reaction product, the pouring part in ice water and analysis of the obtained oil layer by the method of gas chromatography.

In properities the way to the reactor, for example an autoclave equipped with an electromagnetic stirrer, serves a predetermined amount of anhydrous HF and a predetermined number BF3. While stirring the contents of the liquid temperature kept in the range from 35 to 70C. the pressure in the reactor increases, for example, to a value in the range from 0.5 to 3 MPa in the submission to him of carbon monoxide. After that, in accordance with the need to maintain the pressure in the reactor serves monoxide. Within one hour the reactor was filed 2,6-DMN dissolved in the solvent. Within 20 minutes the mixture is kept under these conditions, the result can be obtained 2,6-DMAL. The formation of 2,6-DMNL can be confirmed in the result of the selection of the sample, the hour and the liquid reaction product, pouring part in ice water and analysis of the obtained oil layer by the method of gas chromatography.

In a continuous manner in a reactor such as an autoclave, equipped with an electromagnetic stirrer, serves aliquot of anhydrous HF and an aliquot BF3. While stirring the contents of the liquid temperature kept in the range from 35 to 70C. the pressure in the reactor increases, for example, to a value in the range from 0.5 to 3 MPa in the submission to him of carbon monoxide. After that, in accordance with the need to maintain the pressure in the reactor serves monoxide. Then into the reactor continuously served 2,6-DMN dissolved in the solvent. Into the reactor continuously or periodically submit the remaining parts of anhydrous HF and BF3. The reaction mixture remains in the reactor for a period of time ranging from 1 to 5 hours. Then the liquid reaction mixture is continuously discharged into water with ice. In the analysis of the obtained oil layer by the method of gas chromatography to confirm the receipt of 2,6-DMAL.

The thus obtained liquid reaction mixture is a solution of HF containing complex formed from 2,6-DMAL and catalyst HFBF3and the complex formed from 3,7-DMAL and catalyst HFBF3. As a result of heating the relationship between Agdam DMNL and catalyst HFBF 3is broken, then HF and BF3can be allocated as a result of evaporation and sent for recycling. Thermal decomposition of the complexes is carried out with maximum speed to prevent the passage of thermal decomposition, isomerization, and the like for the received products. Therefore, thermal decomposition of the complexes is preferably carried out under boiling conditions flavobacteria solvent such as a saturated aliphatic hydrocarbon (e.g., heptane) or aromatic hydrocarbons (e.g. benzene), and the solvent is inert to the catalyst HFBF3.

2,6-DMNL can be isolated from the liquid reaction mixture and purified by conventional methods of purification of organic compounds, such as distillation or column chromatography.

Examples

Hereinafter the present invention will be described in detail by means of examples, which should not be construed as limitations of the invention. It should be noted that used the following conditions of the analysis by the method of gas chromatography.

[The conditions of the analysis by the method of gas chromatography]

Chromatograph: GC-17A (a product from the company Shimadzu Corporation)

Used column: HR-1, capillary column (diameter: 0.32 mm x length: 25 the, the product from the company Shinwa Chemical Industries Ltd.)

Condition analysis: inlet temperature of 310C and the detector temperature 310C

The column temperature from 100C to 320C, increased at 5C/min

Detector: flame-ionization detector (PID)

Example 1

In the autoclave with a volume of 1000 ml (made of steel SUS 316L), equipped with a thermostat and an electromagnetic stirrer, was added 2,6-DMN (product of Mitsubishi Gas Chemical Company, Inc.) (100.0 g, 0.64 mol), n-heptane (100.0 g), anhydrous HF (320,2 g, 16.0 mol; when calculating moth on a 25-fold amount in comparison with the amount of 2,6-DMN) and BF3(47,8 g, 0.70 mol; in calculating the moles approximately 1.1-fold amount in comparison with the amount of 2,6-DMN). The liquid temperature was kept equal to 50C. while stirring the content. The pressure in the autoclave was increased to 2 MPa in the submission to him of carbon monoxide. Condition (2 MPa and 50C) was kept for one hour. After that, the obtained reaction mixture were removed and poured into ice water, followed by neutralization to obtain, thereby, the oil layer. As was established in the analysis of the oil layer by the method of gas chromatography, the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 75.6%, and 45.5% and 18.6% (2,6-DMNL/3,7-DMAL = 71,0/29,0), respectively.

In affect, the resulting liquid was subjected to fractional distillation, perepiska through the distillation column (theoretical stage: 20), and received the majority faction (of 38.7 g)containing 2,6-DMNL (71,0% (mass.)) and 3.7-DMNL (28,0% (mass.)) (2,6-DMNL/3,7-DMAL = 71,7/28,3) (2,6-DMNL output 32,8%with a purity of 71.0 per cent). It should be noted that upon completion of the distillation the ratio of isomers is not changed.

Example 2

Repeating the method of example 1 except for the replacement of anhydrous HF (320,2 g, 16.0 mol) in anhydrous HF (384,3 g, 19.2 mol; in calculating the moles 30-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 66.0%, 44.9% and 8.3% of (2,6-DMNL/3,7-DMAL = 84,4/15,6).

Example 3

Repeating the method of example 1 except for the replacement of anhydrous HF (320,2 g, 16.0 mol) in anhydrous HF (384,3 g, 19.2 mol; in calculating the moles 30-fold amount in comparison with the amount of 2,6-DMN) and keeping the liquid temperature of 50C. for 3 hours instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 93.5%, and 48.8% and 7.1% (2,6-DMNL/3,7-DMAL = 87,3/12,7).

p> Example 4

Repeating the method of example 1 except for keeping the liquid temperature is 60C, for 1 hour instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 84.2 per cent, or 37.4% and 6.1% (2,6-DMNL/3,7-DMAL = 85,9/14,1).

Comparative example1

Repeating the method of example 1 except for the replacement of anhydrous HF (320,2 g, 16.0 mol) in anhydrous HF (42,3 g, 2.1 mol; in calculating the moles of approximately 3.3-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 80.9 per cent, 12.1 per cent and 25.2 per cent (2,6-DMNL/3,7-DMAL = 32,4/67,6).

Thus, in the case of reducing the amount of HF in calculating the moles to less than 5-fold in comparison with the amount of 2,6-DMN, 3,7-ratio significantly exceeded 30% (mol.), and the output of 2,6-DMNL decreased.

Comparative example 2

Repeating the method of example 1 except for keeping the liquid temperature equal to 25C. for 3 hours instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatograph is I. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal 77,0%, 30.6 per cent and 37.4% (2,6-DMNL/3,7-DMAL = 45,0/55,0).

Thus, in the case of raising the reaction temperature to less than 35C, 3,7-ratio significantly exceeded 30% (mol.).

Comparative example 3

Repeating the method of example 1 except for keeping the liquid temperature of 75C. for 1 hour instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 90.2 per cent, 10.3 per cent and 0.8 per cent (2,6-DMNL/3,7-DMAL = br93.1/6,9).

Thus, in the case of raising the reaction temperature to more than 70C, in the form of by-products received large amounts of high-boiling compounds, thus, significantly reduced the yield of 2,6-DMAL.

Comparative example 4

Repeating the method of example 1 except for the replacement BF3(47,8 g, 0.70 mol) in BF3(14.3 g, 0.21 mol; in calculating the moles of approximately 0,33-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMN the L were equal to 33.6%, 5,2% and 13.5% (2,6-DMNL/3,7-DMAL = 27,8/72,2).

Thus, in the case of reducing the number BF3in calculating the moles to less than 0.5-fold in comparison with the amount of 2,6-DMN, the percentage degree of conversion of 2,6-DMN decreased; output 2,6-DMNL significantly decreased, and 3,7-ratio significantly exceeded 30% (mol.).

Example 5

Repeating the method of example 1 except for the replacement of materials feedstock 2,6-DMN (100.0 g, 0.64 mol), n-heptane (100.0 g) and BF3(47,8 g, 0.70 mol) of materials feedstock 2,6-DMN (50.0 g, 0.32 mol), n-heptane (50.0 g) and BF3(23.9 g, 0.35 mol; in calculating the moles approximately 1.1-fold amount in comparison with the amount of 2,6-DMN) (i.e., HF/2,6-DMN = at approximately 50 per moth) and keeping the temperature of the liquid equal to 40C. for 5 hours instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 91.6%, 45.2% and 18.9 per cent (2,6-DMNL/3,7-DMAL = 70,5/29,5).

Example 6

Repeating the method of example 1 except for the replacement of anhydrous HF (320,2 g, 16.0 mol) in anhydrous HF (128,1 g, 6.4 mol; in calculating the moles approximately 10-fold amount in comparison with the amount of 2,6-DMN) and keeping the liquid temperature of 0C, within 3 hours instead of 50C for 1 hour. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 96.3%, 40.8% and 17.4% (2,6-DMNL/3,7-DMAL = 70,1/29,9).

Comparative example 5

Repeating the method of example 6 except keeping the liquid temperature is 10C, for 5 hours instead of 50C for 3 hours. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal 89,7%, 21.1% and 60.1% of (2,6-DMNL/3,7-DMAL = 26,0/74,0).

In the case of reaction at 10C, which corresponds to the temperature range of the reaction, generally used in the known method the reaction using the catalyst HFBF3has achieved a high percentage of the degree of conversion of 2,6-DMN, but the output 2,6-DMNL decreased, and 3,7-ratio significantly exceeded 30% (mol.).

Comparative example 6

Repeating the method of example 6 except for keeping the temperature of the liquid, equal to 30C. for 5 hours instead of 50C for 3 hours. The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found, p is acenta the degree of transformation of 2,6-DMN, output 2,6-DMAL and output 3,7-DMNL were equal to 21.5%13.6% and 7.3% of (2,6-DMNL/3,7-DMAL = 65,0/35,0).

In the case of reaction at 30C, which corresponds to the temperature range of the reaction, generally used in the known method the reaction using the catalyst HFBF3interest degree of conversion of 2,6-DMN decreased, and the output of 2,6-DMNL decreased significantly.

Comparative example 7

Repeating the method of example 6 except for replacing BF3(47,8 g, 0.70 mol) in BF3(295,2 g, 4.35 mol; in calculating the moles of approximately 6,8-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 2.5%, 1.1% and 1.0% of (2,6-DMNL/3,7-DMAL = 54,0/46,0).

Thus, in the case of reaction at 30C, which corresponds to the temperature range of the reaction, generally used in the known method the reaction using the catalyst HFBF3and a significant excess number BF3,in calculating the moles, a 3.5-fold amount in comparison with the amount of 2,6-DMN percentage degree of conversion of 2,6-DMN significantly decreased, and significantly decreased the yield of 2,6-DMAL.

Example 7

Repeated m is todoku example 1 except for the replacement BF 3(47,8 g, 0.70 mol) in BF3(143,4 g, 2.10 mol; in calculating the moles of approximately 3.3-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal 58,5%, and 29.7% and 10.2% (2,6-DMNL/3,7-DMAL = 74,4/25,6).

Comparative example 8

Repeating the method of example 1 except for the replacement BF3(47,8 g, 0.70 mol) in BF3(191,2 g, 2.82 mol; in calculating the moles estimated 4.4-fold amount in comparison with the amount of 2,6-DMN). The resulting oil layer was analyzed by the method of gas chromatography. As a result, it was found that the percentage degree of conversion of 2,6-DMN, the yield of 2,6-DMAL and output 3,7-DMNL were equal to 33.3%, 11.5% and 4.4% of 2,6-DMNL/3,7-DMAL = 72,3/27,7).

Thus, in the case of some of the excess amount BF3when calculating on the mole, a 3.5-fold amount in comparison with the amount of 2,6-DMN output 2,6-DMNL significantly decreased.

Applicability in industry

2,6-dimethyl-1-naphthaldehyde obtained by the method of the present invention is suitable for use in industrial chemical materials, materials of raw materials for pharmaceutical products, pesticides, optical function of the national materials electronic functional materials and the like.

The way to obtain 2,6-dimethyl-1-naphthaldehyde involving formirovanie 2,6-dimethylnaphthalene with carbon monoxide, wherein formirovanie carried out in the presence of hydrogen fluoride in calculating the moles in a quantity ranging from 5 - to 100-fold and boron TRIFLUORIDE in calculating the moles in amounts in the range from 0.5 to 3.5 times the quantity, in comparison with the amount of 2,6-dimethylnaphthalene and at the reaction temperature in the range from 35 to 70C.



 

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6 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing glycol aldehyde, involving reaction of formaldehyde with hydrogen and carbon monoxide in the presence of a catalyst composition, which is based on a) rhodium source, b) ligand with general formula R1P-R2 (I), where R1 is a bivalent radical, which, together with the phosphorous atom to which it is bonded, is 2-phospha-1,3,5,7-tetraC1-20alkyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decile group, and where R2 is a monovalent radical, which is chosen from an alkyl group, containing 4 to 34 carbon atoms or a radical with general formula: -R3-C(O)NR4R5 (II), where R3 represents methylene, ethylene, propylene or butylene, and R4 and R5 independently represent an alkyl group containing 1 to 22 carbon atoms, and c) anion source. The invention also relates to a catalyst composition used in the production of glycol aldehyde, and to a method of producing ethylene glycol from glycol aldehyde obtained using the described method.

EFFECT: easy conversion of formaldehyde to glycol aldehyde in the presence of a stable catalyst.

6 cl, 11 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 2,6-dimethyl-1-naphthaldehyde which is used in industrial chemical materials and raw materials for pharmaceutical products, pesticides, optical functional materials and electronic functional materials. The method involves formylation of 2,6-dimethylnaphthalene with carbon monoxide in the presence of hydrogen fluoride in terms of moles in amount ranging from 5- to 100-fold and boron trifluoride in terms of moles in amount ranging from 0.5- to 3.5-fold compared to the amount of 2,6-dimethylnaphthalene, and at reaction temperature ranging from 35 to 70C.

EFFECT: method enables to obtain and end product with high selectivity.

15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 4-(4-alkylcyclohexyl)benzaldehyde or 4-(cyclohexyl)benzaldehyde, which can be used in chemical products used in materials for electronic equipment, including liquid crystals, and for pharmaceutical and agrochemical application. The invention also relates to versions of a method of producing 4-(trans-4-alkylcyclohexyl)benzaldehyde and a method of producing (trans-4-alkylcyclohexyl)benzene. The method of producing 4-(4-alkylcyclohexyl)benzaldehyde or 4-(cyclohexyl)benzaldehyde involves formylation of a benzene derivative of formula (1a) with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride where R1 denotes an alkyl group containing 1-10 carbon atoms or a hydrogen atom. The hydrogen fluoride is used in amount of not less than 3 moles but not more than 20 moles, and boron trifluoride is used in amount of not less than 1.1 moles but not more than 5 moles per mole of the benzene derivative of formula (1a), and formylation is carried out at temperature from -50C to 30C.

EFFECT: invention enables selective synthesis of desired products with high purity.

10 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method for obtaining 4,4'-diformyldiphenylalkane, represented by means of the following formula (2), which is suitable as different industrial chemical initial substances and in production of initial substances for medications, agrochemicals, optic and electronic functional materials. Method includes formylation of diphenylalkane, represented by means of the following formula (1), with carbon monoxide in presence of fluorohydrogen and boron trifluoride, in which temperature of formylation reaction constitutes from -50 to 5C, from 5 to 30 mol of fluorohydrogen are used per 1 mol of diphenylalkane and from 1.5 to 5 mol of boron trifluoride are used per 1 mol of diphenylalkane:

in which R represents alkanediyl group, containing from 1 to 6 carbon atoms, in which R represents alkanediyl group, containing from 1 to 6 carbon atoms.

EFFECT: claimed method makes it possible to obtain target products with high degree of purity and with high output.

6 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel aromatic aldehyde represented by the formula

having a branched alkyl group containing from 10 to 14 carbon atoms and to the method for its production, to an epoxy resin curing composition comprising a polyamine compound and the claimed aromatic aldehyde, to the compositions based on epoxy resin for coating, of civil engineering and construction, containing the claimed curing composition, to the cured coating film and to the cured material. In formula (II), each of the groups R1 and R2 independently represents an alkyl group having 1 to 12 carbon atoms, and the total number of carbon atoms in the groups R1 and R2 is from 9 to 13.

EFFECT: improving the properties of aldehyde.

9 cl, 12 dwg, 2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 2,6-dimethyl-1-naphthaldehyde which is used in industrial chemical materials and raw materials for pharmaceutical products, pesticides, optical functional materials and electronic functional materials. The method involves formylation of 2,6-dimethylnaphthalene with carbon monoxide in the presence of hydrogen fluoride in terms of moles in amount ranging from 5- to 100-fold and boron trifluoride in terms of moles in amount ranging from 0.5- to 3.5-fold compared to the amount of 2,6-dimethylnaphthalene, and at reaction temperature ranging from 35 to 70C.

EFFECT: method enables to obtain and end product with high selectivity.

15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 4-(4-alkylcyclohexyl)benzaldehyde or 4-(cyclohexyl)benzaldehyde, which can be used in chemical products used in materials for electronic equipment, including liquid crystals, and for pharmaceutical and agrochemical application. The invention also relates to versions of a method of producing 4-(trans-4-alkylcyclohexyl)benzaldehyde and a method of producing (trans-4-alkylcyclohexyl)benzene. The method of producing 4-(4-alkylcyclohexyl)benzaldehyde or 4-(cyclohexyl)benzaldehyde involves formylation of a benzene derivative of formula (1a) with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride where R1 denotes an alkyl group containing 1-10 carbon atoms or a hydrogen atom. The hydrogen fluoride is used in amount of not less than 3 moles but not more than 20 moles, and boron trifluoride is used in amount of not less than 1.1 moles but not more than 5 moles per mole of the benzene derivative of formula (1a), and formylation is carried out at temperature from -50C to 30C.

EFFECT: invention enables selective synthesis of desired products with high purity.

10 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method for obtaining 4,4'-diformyldiphenylalkane, represented by means of the following formula (2), which is suitable as different industrial chemical initial substances and in production of initial substances for medications, agrochemicals, optic and electronic functional materials. Method includes formylation of diphenylalkane, represented by means of the following formula (1), with carbon monoxide in presence of fluorohydrogen and boron trifluoride, in which temperature of formylation reaction constitutes from -50 to 5C, from 5 to 30 mol of fluorohydrogen are used per 1 mol of diphenylalkane and from 1.5 to 5 mol of boron trifluoride are used per 1 mol of diphenylalkane:

in which R represents alkanediyl group, containing from 1 to 6 carbon atoms, in which R represents alkanediyl group, containing from 1 to 6 carbon atoms.

EFFECT: claimed method makes it possible to obtain target products with high degree of purity and with high output.

6 cl, 1 tbl, 8 ex

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