JPS58201744A - Preparation of vinyl-substituted cyclohexenedicarboxaldehyde - Google Patents

Abstract

PURPOSE:To obtain the titled compound consisting of a novel substance useful as a raw material for organic industrial products efficiently in high purity, by oxidizing a 5C chain compound having CH3 in the side chain in the vapor phase in the presence of a metallic oxide, e.g. Mo-Bi-Tl type, etc. as a catalyst. CONSTITUTION:A 5C chain compound having CH3 in the side chain s oxidized in the vapor phase with molecular oxygen in the presence of a metallic oxide catalyst of formula I (Xc are one or more elements selected from a metallic element of Group I or a metallic element of Group II in the periodic table and Tl; a, b, c and d are the numbers of atoms of Mo, Bi, X and O; b is 0.01-50; c is 0.01-30 and d is the number of O atoms satisfying the valences of the other atoms) to give aimed compound consisting essentially of 5-vinyl-1-cyclohexene- 1,5-dicarboxaldehyde of formula II which is a novel substance useful as a raw material for flavorous substance like beefsteak plant or a raw material for various organic chemicals. EFFECT:The reaction can be carried out stably for a long term with a long catalyst life.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing vinyl-substituted cyclohexenedicarpoxaldehyde, and more specifically, the present invention relates to a method for producing vinyl-substituted cyclohexenedicarpoxaldehyde, and more specifically, the present invention relates to a method for producing vinyl-substituted cyclohexenedicarpoxaldehyde. The present invention relates to a method for efficiently 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 il + molybdenum and (2) bismuth, iron, or phosphorus (% Kaisho). 52-25747).

According to this method, 4-vinyl-1-cyclohexene-1, which has a perilla-like aroma, is produced from isoprene as a starting material.
4-dicarboxaldehyde (hereinafter referred to as dialdehyde I) can be synthesized in one step. However, in the case of this method, the starting material is limited to isoprene, and the dialdehyde produced is limited to dialdehyde. Therefore, the present inventors synthesized a structural isomer of dialdehyde I that could not be achieved using conventional techniques. As a result of intensive studies to achieve this goal, it was discovered that the use of a catalyst containing a third component in addition to molybdenum and bismuth was extremely effective, leading to the completion of the present invention. is a new substance, vinyl-substituted vinyl-substituted dicarboxaldehyde, whose main component is 5-vinyl-1-cyclohexene-1,5-dicarboxaldehyde (hereinafter referred to as dialdehyde), with high purity and economy. It is therefore an object of the present invention to provide a method for producing carbon atoms having one methyl group in the side chain.
The chain compound (hereinafter referred to as the main reaction raw material) is selected from the group consisting of 111 molybdenum, (2) bismuth, (3) metal elements of Group I, metal elements of Group II of the periodic table, and thallium. This is achieved by gas phase oxidation with molecular oxygen in the presence of a metal oxide catalyst consisting of at least one metal and (4) oxygen.

The main reaction raw materials used in the present invention may be any chain olefins, diolefins, alcohols, and aldehydes having 5 carbon atoms and having a methyl group in the side chain, and a specific example thereof is 2-methylbutene- 1,2-
Methylbutene-2,3-methylbutene-1, Inglene, 2-methyl-1-butanol, t8rt-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
-buten-1-ol, 3-methyl-2-butene-2
-ol, 3-methyl-2-buten-1-ol, 2-
Examples include methyl-3-oten-2-ol, 2-methyl-3-buten-1-ol, -butanediol, α,β-dime3-methyl-16-thylacrolein, and β,β-dimethylacrolein. 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-mentioned four types of elements as essential components, and is usually represented by the general formula CI).

Moa Blb Xc −Oa −−・−= C
I) (Here, X represents one or more elements selected from Group ■ metal elements, Group ■ metal elements, and T/ of the periodic table,
! L, b, a and d are the number of atoms of Mo, Bi, -X and 0 respectively, and when a-12, b=0.0
1 to 50, O=0.01 to 50, and d is the number of oxygen atoms satisfying the valences of other elements. ) Among these X elements, especially metal elements of group A, ■a
Metals and metals show good performance.

In addition to these components, other metal elements such as Pa, Ni, Oo, P, B, Mn+Or may be added as necessary.

To, W, Sb, V, As, Nb, Ta, Pb, Sn,
Zr, In.

One or more of La, Os, N4.8m, Th, U, etc. can be added as appropriate, especially Fe, Ni
.

Oo, P, Mn, Or, W+ 8 b, -Pb
By adding one or more metal elements selected from and an, 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 the 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. In addition, the use of a silicon-containing compound such as silicon molybdic acid does not have a negative effect on the catalyst activity. A calcination treatment is carried out using catalyst raw materials for the purpose of converting them into the catalyst of the present invention or activating the catalyst. is normally 500 to 9'00 C while flowing a gas containing molecular oxygen.

It is preferably carried out at 450 to 700 C for about 4 to 16 hours. Alternatively, if necessary, a primary calcination treatment may be performed at a temperature below this calcination temperature, and then a calcination 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 glue. 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, quartz clay, silicon carbide, alumina, pumice, silica-alumina, bentonite, zirconia, zeolite, talc, and refractories. Preferred is a carrier comprising: At this time, the amount of carrier can be appropriately selected. The catalyst can be in the form of powder or tablets, and can be used in any fixed bed, moving bed or fluidized bed method.

In the present invention, the reaction between the main reaction raw material and molecular oxygen is carried out in accordance with the conventional method used in chemical reactions, except for the use of 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.).

Further, the reaction temperature is 250 to 700Us, preferably 500Us.
~600C, reaction pressure is normal pressure ~10 atm, contact time of all feedstock gases is 0.3~20 seconds (NTP standard), reaction main material concentration in feedstock gas is 0.5~25vol., reaction main material vs. The oxygen ratio is 1:0.5-40, and the preferred supply gas composition is reaction main raw material: air: steam M1:3-50 = D-5
0 (molar ratio).

Thus, according to the present invention, it is possible to obtain a dialdehyde mixture containing dialdehyde (III) with good selectivity from various easily available raw materials, and if necessary, this mixture can be treated according to conventional methods. The catalyst system used in the present invention has a long catalyst life and can carry out stable reactions over a long period of time.

Incidentally, dialdehyde (2) is a substance represented by the following structural formula [11], and like dialdehyde (2), it is useful as a sin-like aromatic substance, and is also useful as a raw material for various organic drugs.

HO 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 t・rt-amyl alcohol is used as a raw material, 2-methyl-butene-2-methyl-butene- 1,2-Methyl-butene-2 and isoprene, etc., which were produced) could be reused as the main raw materials for the reaction, so they were treated as unreacted materials. The target dialdehyde is a mixture of dialdehyde ① and dialdehyde I.

The structure of dialdehyde can be determined using gas-mass method, elemental analysis, infrared absorption analysis, IH-NMR and I! (3-NMR
It was done by

Example 1: Add bismuth nitrate 291? A solution prepared by dissolving 2.029 m of potassium nitrate in 400 mj of nitric acid aqueous solution was added with sufficient stirring, and the mixture was evaporated to dryness. This is 120
After drying at C for 8 hours, primary firing was performed at 550C for 4 hours in an air stream, and the obtained primary fired product was pulverized to 100 meshes or less. After about 50% by weight of this was attached to a spherical silicon carbide carrier with a diameter of 4 ms,
The composition of the elements (the same applies hereinafter) excluding oxygen and the carrier of the catalyst obtained after firing at 00C for 2 hours and further at 550C for 6 hours is expressed as MO12BidKa2. length 60
Fill a stainless steel reaction tube with r:m and heat in a metal bath at 450
C and a feed gas having a molar ratio of tart-amyl alcohol:air:steam of 2:20 near B was passed through it at a space velocity of s o o ohr-'. As a result, the reaction rate of main raw materials was 55%, and the dialdehyde selectivity was 35%.
A friend of mine.

Note that dialdehyde l[1j90.
The remaining amount 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, each catalyst was subjected to a reaction in the same manner as in Example 1, and the results shown in Table 1 were obtained. Incidentally, in all Examples, the main product was dialdehyde (2).

Table 1 Examples 15 to 23 Reactions were carried out in the same manner as in Example 1, except that various main reaction materials were used for the tert-amyl alcohol mixture, and the results shown in Table 1 and Table 2 were obtained. Incidentally, in all Examples, the main product was dialdehyde (2).

Table 2 Patent applicant: Zeon Corporation

Claims (1)

[Claims] t A chain compound with 5 carbon atoms having one methyl group in the side chain (υ molybdenum, (21 bismuth, ζ) group I metal elements of the periodic table, group Process G for producing vinyl-substituted cyclohexenedicarboxaldehyde, characterized by gas phase oxidation with molecular oxygen in the presence of a metal oxide catalyst consisting of at least one metal selected from the group consisting of (4) oxygen.