JPH0245611B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing vinyl-substituted cyclohexenedicarboxaldehyde, and more specifically, the present invention relates to a method for producing vinyl-substituted cyclohexene dicarboxaldehyde, and more specifically, it is possible to efficiently produce vinyl-substituted cyclohexene dicarboxaldehyde by gas-phase oxidation of a chain unsaturated hydrocarbon, alcohol, or aldehyde having 5 carbon atoms having a methyl substituent in the side chain. The present invention generally relates to a method for producing vinyl-substituted cyclohexene dicarboxaldehyde. Vinyl-substituted cyclohexene dicarboxaldehyde (hereinafter simply referred to as dialdehyde) is a cyclohexene compound having two formyl groups and one vinyl group in the molecule, and is a compound useful as a raw material for organic industrial products. As a method for synthesizing such dialdehydes, a method is conventionally known in which isoprene is oxidized in the gas phase in the presence of an oxide catalyst consisting of (1) molybdenum and (2) bismuth, iron, or phosphorus. (No. 52-25747). According to this method, 4-vinyl-1-cyclohexene-1,4-dicarboxaldehyde (hereinafter referred to as dialdehyde) having a perilla-like aroma can be synthesized in one step using isoprene as a starting material. However, this method has problems such as the starting material being limited to isoprene and the dialdehyde produced being limited to dialdehyde. Therefore, as a result of intensive research in order to solve the problems of the prior art, the present inventor found that by using a catalyst containing molybdenum, bismuth and a specific third component, dialdehydes and dialdehyde structures can be obtained from easily available raw materials. discovered that isomers could be synthesized,
Based on this knowledge, we have completed the present invention. That is, the main object of the present invention is to obtain a vinyl-substituted compound containing dialdehyde and 5-vinyl-1-cyclohexene-1,5-dicarboxaldehyde (hereinafter referred to as dialdehyde), which is a structural isomer of dialdehyde, as a main component. It is an object of the present invention to provide a method for economically producing cyclohexene dicarboxaldehyde with high purity. , alcohol or aldehyde (hereinafter referred to as
(1) molybdenum, (2) bismuth, (3) at least one metal selected from the group consisting of group metal elements of the periodic table, group metal elements, and thallium; and (4) This is achieved by gas phase oxidation with molecular oxygen in the presence of a metal oxide catalyst consisting of oxygen. The main reaction raw materials used in the present invention are unsaturated hydrocarbons such as chain olefins and diolefins having 5 carbon atoms having a methyl group in the side chain;
Any alcohol or aldehyde may be used; a specific example is 2-methylbutene-
1,2-methylbutene-2,3-methylbutene-
1, isoprene, 2-methyl-1-butanol,
tert-amyl alcohol, 2-methyl-3-butanol, 3-methyl-1-butanol, 3-methyl-3-buten-1-ol, 3-methyl-3-
Buten-2-ol, 2-methyl-2-butene-
1-ol, 3-methyl-2-buten-2-ol, 3-methyl-2-buten-1-ol, 2-
Methyl-3-buten-2-ol, 2-methyl-
3-buten-1-ol, 3-methyl-1,3-
Examples include butanediol, α,β-dimethylacrolein, β,β-dimethylacrolein, and the like. These reaction main raw materials do not necessarily need to be used alone, and can also be used in the form of a mixture thereof or a mixture with other impurities. On the other hand, the catalyst used in the present invention contains the above four elements as essential components, and is usually represented by the general formula [ ]. _{Mo a Bi b} are respectively Mo and
It is the number of atoms of Bi,
is the number of oxygen atoms that satisfies the valences of other elements. ) Among such X elements, group a metal elements, group a metal elements, and Tl exhibit particularly good performance. In addition to these components, other metal elements such as Fe, Ni, Co, P, B, Mn,
Cr, Te, W, Sb, V, As, Nb, Ta, Pb, Sn,
One or more of Zr, In, La, Ce, Nd, Sm, Th, U etc. can be added as appropriate, especially Fe, Ni, Co, P, Mn, Cr, W, Sb, Pb and
By adding one or more metal elements selected from Sn, the catalytic performance can be greatly improved. The catalyst used in the present invention can be prepared by various methods known in the art, such as evaporation to dryness, oxide mixing, coprecipitation, and the like. As raw materials for each element used in the preparation of the catalyst, not only oxides but also any material can be used as long as it forms the catalyst of the present invention by calcination. Examples of these include salts such as ammonium salts, nitrates, carbonates, organic acid salts, and halides of each element, free acids, acid anhydrides, condensed acids, and heteropolyacids containing molybdenum such as silicomolybdic acid. Examples include heteropolyacid salts such as ammonium salts and metal salts. Furthermore, the use of silicon-containing compounds such as silicomolybdic acid does not adversely affect the catalyst activity. The calcination treatment carried out for the purpose of converting the catalyst raw material into the catalyst of the present invention or activating the catalyst is usually performed at a temperature of about 300 to 900°C, preferably 450 to 700°C, under the flow of a gas containing molecular oxygen. It lasts from 4 hours to 16 hours.
Further, if necessary, a primary firing treatment may be performed at a temperature equal to or lower than this firing temperature, and then a firing treatment may be performed at the above temperature. The catalyst of the present invention can be used as it is, but it can also be used by attaching it to a carrier of an appropriate shape or diluting it with a carrier (diluent) in the form of powder, sol, or gel. You can also do it.
As the carrier or diluent, known carriers or diluents may be used, such as titanium dioxide, silica gel, silica sol, diatomaceous earth, silicon carbide, alumina, pumice, silica-alumina, bentonite, zirconia, zeolite, talc, and refractories. A carrier containing is preferred. At this time, the amount of carrier can be appropriately selected. The catalyst can be in a suitable form as powder or tablets and can be used in any fixed bed, moving bed or fluidized bed method. The reaction between the main reaction raw material and molecular oxygen in the present invention is carried out according to a conventional method used in gas phase catalytic oxidation reactions, except for using the above-mentioned novel catalyst. For example, the source of molecular oxygen does not necessarily have to be highly pure oxygen; air is generally practical. If necessary, it can be diluted with an inert gas that does not adversely affect the reaction (for example, water vapor, nitrogen, argon, carbon dioxide, waste gas after removing useful substances from the reaction product, etc.). Furthermore, the reaction temperature is 250-700℃, preferably
300 to 600℃, reaction pressure is normal pressure to 10 atm, contact time of all feed gases is 0.03 to 20 seconds (NTP standard), concentration of reaction main material in feed gas is 0.5 to 25% by volume,
The reaction main raw material to oxygen ratio is 1:0.5 to 40, and the preferred supply gas composition is reaction main raw material: air: water vapor = 1:3.
~30:0~50 (molar ratio). Thus, according to the present invention, dialdehydes and dialdehyde mixtures consisting of dialdehydes can be obtained with high selectivity from various easily available raw materials, and if necessary, by treating this mixture according to conventional methods. Dialdehydes and dialdehydes can be isolated with high purity. Furthermore, the catalyst system used in the present invention has a long catalyst life and can perform stable reactions over a long period of time. Incidentally, dialdehyde is a substance represented by the following structural formula [], and like dialdehyde, it is useful as a perilla-like aromatic substance, and is also useful as a raw material for various organic drugs. The present invention will be explained in more detail with reference to Examples below. The reaction rate and selectivity in the examples were according to the following formula. Note that some of the reaction main raw materials may produce other reaction main raw materials due to the reaction (for example, when tert-amyl alcohol is used as a raw material, 2-methyl-butene-2-methyl-butene- 1,2-methyl-
Butene-2, isoprene, etc. were also produced), and these were treated as unreacted substances because they could be reused as the main raw materials for the reaction. The target dialdehyde is a mixture of dialdehydes and dialdehydes. Main reaction raw material reaction rate (%) = Reacted main reaction material (mol) / Supplied reaction main material (mol) x 100 Dialdehyde selectivity (%) = 2 x Dialdehyde produced (mol) / Reacted main material Raw material (mol) x 100 The structure of dialdehyde was determined using the gas-mass method, elemental analysis, infrared absorption analysis, ¹ H-NMR
and ¹³ C-NMR. Example 1 To a solution in which 212 g of ammonium molybdate was dissolved in 400 ml of warm water, a solution in which 291 g of bismuth nitrate and 2.02 g of potassium nitrate were dissolved in 400 ml of an aqueous nitric acid solution was added with thorough stirring, and the mixture was evaporated to dryness. this
After drying at 120°C for 8 hours, primary firing was performed at 350°C for 4 hours in an air stream, and the obtained primary fired product was pulverized into 100 meshes or less. Approximately 30% by weight of this was attached to a spherical silicon carbide carrier with a diameter of 4 mm, and then heated at 400°C for 2 hours in an air stream and then at 550°C for 6 hours.
Baked for an hour. The elemental composition (the same applies hereinafter) of the obtained catalyst excluding oxygen and the carrier is shown as Mo ₁₂ Bi ₆ K _0.2 . 50ml of the catalyst obtained in this way has an inner diameter of 2.5cm and a length of
Fill a 60cm stainless steel reaction tube and place in a metal bath.
It was heated to 450° C. and a feed gas having a molar ratio of tert-amyl alcohol:air:steam of 2:20:78 was passed through it at a space velocity of 3000 hr ⁻¹ . As a result, the reaction rate of the main raw material was 55%, and the dialdehyde selectivity was
It was 35%. In addition, dialdehyde in dialdehyde is
The amount was 90.4 mol%, and the remainder was dialdehyde. Examples 2 to 14 Catalysts shown in Table 1 were prepared in the same manner as in Example 1 except that the component X and the composition ratio were changed. Next, a reaction was carried out using each catalyst in the same manner as in Example 1, and the results shown in Table 1 were obtained. In addition, in all Examples, the production ratio with dialdehyde was comparable to that in Example 1.

[Table] Examples 15 to 23 Reactions were carried out in the same manner as in Example 1, except that various main reaction materials were used instead of tert-amyl alcohol, and the results shown in Table 2 were obtained. In addition,
In all Examples, the production ratio with dialdehyde was comparable to that in Example 1.

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Claims (1)

[Claims] 1 Chain-like unsaturated hydrocarbons, alcohols, or aldehydes with 5 carbon atoms having one methyl group in the side chain are combined with (1) molybdenum, (2) bismuth, (3) group metal elements of the periodic table, and group metal elements of the periodic table. at least one metal selected from the group consisting of group metal elements and thallium; and
(4) A method for producing vinyl-substituted cyclohexene dicarboxaldehyde, which is characterized by gas phase oxidation with molecular oxygen in the presence of a metal oxide catalyst consisting of oxygen.