JPH05310631A - Production of 1,6-hexanedial - Google Patents

Abstract

PURPOSE:To profitably obtain 1,6-hexanedial useful as an intermediate for chemicals through 2-hexene-1,6-dial by dimerizing easily available 1-propene-3-al as a raw material in the presence of a catalyst comprising an organic VIII group metal compound. CONSTITUTION:1-Propene-3-al is dimerized in the presence of a dimerizing catalyst of an organic VIII metal compound [e.g. 8eta-cyclooctadiene)(eta-toluene) ruthenium] to obtain 2-hexene-1,6-dial. The compound is hydrogenated in the presence of a reduction catalyst (e.g. a platinum group metal such as Pt or Pb, or its combination with a carrier such as C or Al) to obtain 1.6-hexanedial. The 1-propene-3-al as a raw material is oxidized with air in the presence of a metal oxide catalyst in a gaseous phase. The 1,6-hexanedial is readily derived into adipic acid as a raw material for polyamides, etc., by an oxidation reaction or into 1,6-diaminohexane by a reductive amination reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing 1,6-hexanediol. 1,6-Hexanedial is converted to adipic acid, which is a raw material for polyamide, by an oxidation reaction, and 1,6-hexanedial is converted to 1,6
-It is a very useful chemical intermediate, such as easily induced by diaminohexane.

[0002]

2. Description of the Related Art Conventionally, as a method for producing 1,6-hexanediol, a method of oxidizing 1,2-cyclohexanediol with sodium periodate, lead tetraacetate or the like, or an ozonide produced after ozone oxidation of cyclohexene , A method for producing cyclohexene with osmium tetroxide and sodium periodate, and the like have been reported.

At present, these methods have not been implemented industrially because the raw materials and reagents are expensive and a special reaction apparatus is used. on the other hand,
1-Propene-3-al (acrolein), which is produced on a large scale industrially by air oxidation of propylene
Since it can be manufactured at low cost and has high reactivity, it has been attracting attention as an important intermediate for various organic compounds for a long time (for example, CWSmith, "Acrolein", John Wiley &
Sons, pages 1-27, 1962).

2-hexene-1,6-dial is 1,
It has been reported to be obtained by reacting 3-cyclooctadiene with ozone and dimethyl sulfide (T. Hudlicky et al., Journal of the American Chemic.
al Society, vol.110, p.4735 (1988)). However, in this method, an expensive raw material is used at an extremely low concentration and the reaction is performed at -78 ° C while controlling the ozone concentration, which is not desirable as an industrial production method.

Further, the dimerization reaction of 1-propen-3-al (acrolein) is carried out without a catalyst at 185-1.
By reacting at 95 ° C., 2,3-dihydro-2
-Formylpyran is known to be obtained (Japanese Patent Publication No. 40-9264). It has also been reported that the polymerization reaction proceeds by using a ruthenium compound as a catalyst (S. Komiya et al. Bulletin of the
Chemical Society of Japan, vol.48, 101 (1975))
However, there is no mention of dimer formation of 1-propen-3-al in this paper.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing 1,6-hexanedial suitable for industrial production.

[0007]

According to the present invention, 1-propen-3-al is reacted in the presence of a dimerization catalyst comprising an organic Group 8 metal compound to give 2-hexene-1,6-dial. , It was hydrogenated in the presence of a reducing catalyst to give 1,6-
1,6-, characterized by producing hexanediol
It is a method for producing hexane dial. (Raw material) The raw material 1-propen-3-al is industrially produced by air-oxidizing propylene in the gas phase in the presence of a metal oxide catalyst.

(Dimerization catalyst) In the production method of the present invention, 1
A catalyst is used for the dimerization of propen-3-al. As the dimerization catalyst, an organometallic compound containing at least one of Group 8 metal elements as a constituent component is used. The Group 8 metal is preferably one of iron, ruthenium and osmium, and more preferably ruthenium.

The Group 8 metal is preferably used as an organic metal compound soluble in the raw material. 8th
The organic group that coordinates or bonds to the group metal includes ethene,
Alkenes such as butene, butadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cyclooctadiene, 1,5-cyclooctadiene, 2,
Dienes such as 5-norbornadiene, trienes such as 1,3,5-cyclooctatriene, benzene, toluene, xylene, cumene, p-cymene, hexamethylbenzene, p-methoxybenzene, naphthalene, anthracene, benzonitrile, Examples include arenes such as anisole. The composition ratio of the organic group to the Group 8 metal is 1,000,000 or less, preferably 100,000 or less in terms of molar ratio.

Examples of the organic Group 8 metal compound include (η
-Cyclooctadiene) (η-cyclooctatriene)
Ruthenium, (η-benzene) (η-1,3-cyclohexadiene) ruthenium, bis (ethene) (η-hexamethylbenzene) ruthenium, (η-cyclooctadiene) (η-hexamethylbenzene) ruthenium, (η −
Benzene) (η-cyclooctadiene) ruthenium,
(Η-benzene) (η-norbornadiene) ruthenium, (η-cyclooctadiene) (η-1,3,5-trimethylbenzene) ruthenium, (η-norbornadiene) (η-1,3,5-trimethylbenzene) Ruthenium, (η-cyclooctadiene) (η-toluene) Ruthenium, (η-Cyclooctadiene) (η-xylene)
Ruthenium, (η-p-cymene) (η-cyclooctadiene) Ruthenium, (η-cyclooctadiene) (η-
p-methoxybenzene) ruthenium, (η-cyclooctadiene) (η-cycloheptatriene) ruthenium,
Examples include (η-cycloheptadiene) (η-cycloheptatriene) ruthenium, bis (cyclohexadienyl) ruthenium, and bis (hexamethylbenzene) ruthenium.

The dimerization catalyst can also be prepared by forming an organic Group 8 metal compound in the reaction system. The amount of the dimerization catalyst used is 1-propene-3 as the raw material.
-0.0000001 to 1 (molar ratio), preferably 0.000001 to 0.1 (molar ratio), relative to are
The range is. The dimerization catalyst is separated from the product of the dimerization reaction by a general method such as distillation and extraction and can be used repeatedly.

(Solvent for Dimerization Reaction) The dimerization reaction can be carried out without using any solvent, but if necessary, it is carried out in a suitable solvent that does not react with 1-propen-3-al. can do. Examples of these solvents include water; hydrocarbons such as hexane, benzene, and toluene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; esters such as ethyl acetate, butyl acetate, butyrolactone; dimethylformamide, Examples thereof include amides such as dimethylacetamide and N-methylpyrrolidinone; ureas such as dimethylimidazolidinone and tetramethylurea; alcohols such as isopropanol and t-butanol.
The concentration of 1-propen-3-al in these solvents is
It is 1% by weight or more, preferably 10% by weight or more.

(Dimerization Reaction Conditions) The dimerization reaction sufficiently proceeds even at room temperature, but it may be carried out under heating in order to further improve the reaction rate. The optimum reaction temperature varies depending on the pressure in the system, but generally 0 to 200 ° C,
It is preferably in the range of 20 to 150 ° C. The reaction pressure varies depending on the reaction temperature, but is generally in the range of 1 to 200 bar, preferably 5 to 100 bar. The reaction time varies depending on the reaction temperature, the catalyst concentration and the concentration of the raw materials, but is generally 0.1 to 200 hours, preferably 0.2 to 1
It is in the range of 00 hours.

The reaction can be carried out in air as long as the catalyst does not change, but it is generally carried out under a deoxygenated atmosphere,
Degas to a vacuum or replace with an inert gas such as nitrogen or argon or hydrogen. It is particularly preferable to carry out in the presence of hydrogen. In that case, the hydrogen pressure is generally in the range of 0.1 to 200 bar, preferably 0.5 to 100 bar, though it varies depending on other reaction conditions such as temperature.
The hydrogen used does not necessarily have to be of high purity, and substances that do not inhibit this reaction, such as nitrogen,
Argon, methane, etc. may be mixed with hydrogen at an arbitrary ratio and used.

(Product of Dimerization Reaction) 2-Hexene-1,6-dial is obtained by the above dimerization reaction.
At the same time, 2-methylenepentane-1,5-diar, which is an isomer of 2-hexene-1,6-diar, and
Oligomer of trimer or more of 1-propen-3-al may also be produced. The reaction mixture containing the catalyst is separated from the catalyst by a known method such as filtration, distillation, extraction, adsorption, etc. to separate 2-hexene-1,6-dial, and purified as necessary to obtain the next reduction / hydrogen. Subject to chemical reaction.

(Reduction catalyst) In the reduction reaction, a general carbon-carbon double bond hydrogenation catalyst is used. As specific examples, platinum, palladium, ruthenium, platinum group metal simple substances such as rhodium, or these metals are supported on a common carrier such as carbon, aluminum, silica, silica-alumina, magnesia, zirconia, diatomaceous earth. There are things. In the case of a supported catalyst, the amount of metal supported is not particularly limited, but is 0.1 to 20% by weight, preferably 0.5 to 20.
It is in the range of% by weight. The amount of the reducing catalyst used is 0.00001 in terms of weight ratio to 2-hexene-1,6-dial.
˜1, preferably 0.0001 to 0.1.

(Solvent for reduction reaction) The reduction reaction does not require a solvent, but when the need for controlling the heat of reaction arises, the reaction can be carried out in a suitable solvent. Specific examples of these solvents include water; aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene and toluene; methanol, ethanol, propanol,
Aliphatic alcohols such as butanol; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and dioxane can be used, and 1,6-hexanedial, which is a target product, can also be used as a solvent. it can. The amount of the solvent used is such that the concentration of 2-hexene-1,6-dial in the charged reaction solution is 0.1 to 100% by weight, preferably 1 to 100% by weight.

(Reduction reaction conditions) The reduction reaction is carried out in a hydrogen atmosphere in the presence of a hydrogenation catalyst. Reaction conditions such as reaction temperature, time, and hydrogen pressure differ depending on the metal species of the catalyst used. For example, ruthenium catalyst
Under severe conditions, not only the carbon-carbon double bond but also the reduction of the formyl group is promoted, so milder conditions are required. However, general reaction conditions are as follows.

The reaction temperature is in the range of -50 to 200 ° C, preferably -5 to 100 ° C. The reaction pressure is 1-100
It is in the range of 1 bar, preferably 1 to 50 bar. Although pressurization is not always required, it is preferable to carry out under pressurized hydrogen from the viewpoint of reaction efficiency. Hydrogen may be diluted with nitrogen or the like before use. The reaction time varies depending on the reaction temperature, pressure, amount of catalyst, etc., but is about 0.1 to 10 hours.
As the reactor, a generally used reactor such as a complete mixing reactor or a fixed bed reactor can be used.

[0020]

Industrial Applicability According to the production method of the present invention, 1,6-propene-3-al is easily dimerized to obtain 2-hexene-1,6-dial.
-Hexanedial can be produced industrially advantageously.

[0021]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, 2-hexene-1,6-dial was quantitatively analyzed by gas chromatography using an internal standard method using diethylene glycol diethyl ether as an internal standard substance, and the conversion rate and selectivity were determined by the following equations. Conversion rate (%) = 100 × (mol number of reacted raw material / mol number of charged raw material) Selectivity (%) = 100 × (mol number of target substance × 2 / mol number of reacted raw material)

<Example 1> In a Schlenk type flask, 228.7 mg (0.759 mmol) of (η-cyclooctadiene) (η-toluene) ruthenium was added to a Schlenk flask under a nitrogen stream.
8.8731 g (158.3 mmol) of 1-propen-3-al containing 1% by weight of hydroquinone and 0.534 g of diethylene glycol dimethyl ether as an internal standard substance for analyzing the reaction solution were charged. A stirrer was previously placed in a stainless steel autoclave having an inner volume of 30 ml to keep a nitrogen atmosphere, and the solution in the Schlenk type flask was transferred thereto. The inside of the system of this autoclave was replaced with hydrogen gas, hydrogen was introduced under pressure up to 5 bar, and then the reaction was carried out at 70 ° C. for 1 hour. As the reaction progressed, the reaction pressure dropped from 5.5 bar to 3.5 bar.

After completion of the reaction, the autoclave was opened and the contents were analyzed by gas chromatography.
-Propen-3-R 0.521g (2.29mmo
l), (Z) -2-hexene-1,6-dial 3.1
53 g (28.12 mmol), 2-methylene pentane-
0.15-mg (1.39 mmol) 1,5-Dial, 0.118 g (2.04 mmol) propanal, and 0.412 g (2.45 mm) trimer of 1-propen-3-al.
ol) was detected. In addition, oligomers of tetramer or higher of 1-propen-3-al were also produced.

The conversion rate of 1-propen-3-al is 9
It was 4.1%, and the selectivity of (Z) -2-hexene-1,6-diary was 37.8%. The obtained reaction solution was distilled under reduced pressure to capture 2.8 g of a fraction at 78 ° C. at 0.8 mmHg. Analysis by gas chromatography and NMR showed that (Z) -2-hexene-1,6-
The diar content was 90%, and it was found that a small amount of 2-methylenepentane-1,5-dial and 1-propen-3-al trimer was contained.

In a three-necked flask with an internal volume of 50 ml equipped with a gas inlet tube, 0.1319 g of 5% Pd / C catalyst, 5 ml of ethanol as a solvent, and the above-obtained (Z) were obtained.
-2-hexene-1,6-dial fraction 1.28 g
(((Z) -2-hexene-1,6-dial as 1.
0 g (8.9903 mmol)) was charged. A gas holder filled with hydrogen was connected to a gas introduction pipe, the inside of the container was replaced with hydrogen gas, and the mixture was stirred at room temperature for 6 hours.

After confirming the absorption of a stoichiometric amount of hydrogen, the hydrogen gas in the container was evacuated and the catalyst was filtered off. The filtrate was concentrated under reduced pressure, and the obtained oily substance was analyzed by gas chromatography to find that 1,6-hexanediol was 0.97.
69 g (8.56 mmol) had formed ((Z) -2-
The yield based on hexene-1,6-dial is 95.2 mol%). The addition rate of (Z) -2-hexene-1,6-dial was 100%. The identification of the product is
By NMR.

Reference Example 1 Production of 1,6-Diaminohexane Based on the production method of aliphatic diamine described in JP-B-58-26902, reductive amination reaction of 1,6-hexanedial is carried out. To produce 1,6-diaminohexane. (1) Preparation of Schiff base In a 50 ml three-necked flask equipped with a thermometer, a septum cap and a stirrer, 1.2513 g of n-butylamine (1
(7.1 mmol) and 1 ml of toluene were charged, and the mixture was stirred under ice cooling. 1,6-Hexanediol obtained in Example 1
6712 g (5.88 mmol) of 1 ml of toluene was added to
It was added over 1 hour from the septum cap using a syringe. During this time, the temperature of the reactor contents was kept at 5 ° C.
After maintaining at the same temperature for 10 minutes, the temperature was raised to room temperature and stirred for 3 hours to obtain a colorless and transparent two-layer solution.

(2) Production of 1,6-diaminohexane A nickel / diatomaceous earth catalyst of 0.1 was added to a Hastelloy autoclave having an internal volume of 30 ml kept in an argon atmosphere.
878 g and the above two-layer solution were transferred and cooled to -78 ° C in a dry ice-acetone cold bath. After adding 5 ml of liquid ammonia to the reactor and sealing the reactor, 100% hydrogen was added.
The mixture was pressed into a bar and reacted at 120 ° C. for 4 hours.
When the obtained pale yellow uniform reaction liquid was analyzed by gas chromatography, 1,6-diaminohexane 0.5
334 g (4.59 mmol) was produced (yield 78.1 mol% based on 1,6-hexanedial).

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area // B01J 23/40 C07B 61/00 300

Claims (1)

[Claims] 1. The reaction of 1-propen-3-al in the presence of a dimerization catalyst comprising an organic Group 8 metal compound
A process for producing 1,6-hexanedial, which comprises producing hexene-1,6-diial and hydrogenating it in the presence of a reducing catalyst to produce 1,6-hexanedial.