JPH0653692B2 - Process for producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to β-methyl-δ-valerolactone (hereinafter, referred to as MVL) and 3-methylpentane-1,
Regarding a method for producing 5-diol (hereinafter referred to as MPD), specifically, 2-hydroxy-4-methyltetrahydropyran (hereinafter referred to as MHP) is reacted under specific conditions to give MVL and MPD. MVL to be manufactured
And a method for manufacturing MPD.

[Conventional technology]

Conventionally, as a method for producing MVL, β, β-dimethylacrylic acid ethyl ester was used at high temperature in the presence of a cobalt-based catalyst,
A method of treating with a mixed gas of hydrogen and carbon monoxide at high pressure (Chemische Berichte
Vol. 97, 1964, p. 863), or M
Method for oxidative dehydrogenation of PD at a temperature of 200 ° C. in the presence of a copper chromium oxide catalyst (Organic Synt
(See "heses 35", page 87).
In addition, as a method for producing a compound similar to MVL, Bul
l. Chem. Soc. Japan, 35, 986 (1
962) includes 2-hydroxytetrahydropyran (δ-
Oxyvaleraldehyde) is used as a catalyst for copper zinc oxide, copper chromium oxide or copper chromium zinc oxide.
It is described that δ-valerolactone was obtained by continuous gas phase reaction at a temperature of 20 to 230 ° C.

On the other hand, as a method for producing MPD, a method has been proposed in which MHP is hydrogenated in the presence of a hydrogenation catalyst at an elevated temperature and an elevated pressure (see Japanese Patent Publication No. 58-40533).

[Problems to be solved by the invention]

There is no report that the MVL and the MPD are produced at the same time in the conventionally known documents relating to the production of the MVL or MPD. As described above, conventionally, it has not been recognized at all to simultaneously acquire MVL and MPD, and when it is required to acquire both MVL and MPD which are industrially extremely valuable, two independent MVLs and MPDs are required. It has been considered necessary to utilize manufacturing processes. And in fact, in such cases the MVL or MPD was manufactured by a completely separate process.

If MVL and MPD can be efficiently produced at the same time, it is industrially advantageous in that a common raw material and a single reaction can be utilized, and as a result of studying such a production method, the present inventors have determined that MHP can be produced under specific conditions. It was found that MVL and MPD can be produced by reacting in the presence of an oxide catalyst composed of at least one metal selected from copper, chromium and zinc.
A patent application was filed as No. 178928. However, in the above-mentioned invention, MHP is reacted with the product MVL and / or MPD as a reaction solvent to produce MVL.
It was found that a large amount of high-boiling compounds are produced in the case of producing MPD and MPD, which causes a decrease in yield. This problem can be reduced by using about 50% by weight or more of a solvent inert to the reaction, but from an industrial viewpoint, the reaction product itself can be obtained without using a solvent. Reacting as a part of the solvent is extremely advantageous because the solvent recovery is unnecessary and the productivity is high when compared in the same reaction apparatus.

Therefore, an object of the present invention is to provide a highly productive MVL and MPD capable of producing MVL and MPD in a high overall yield in the presence of a solvent using a common raw material and a reaction product as a reaction solvent. To provide a manufacturing method of.

Another object of the present invention is to provide a relatively simple operation.
An object of the present invention is to provide a highly productive industrially advantageous method for producing MVL and MPD, which is capable of producing MVL and MPD with a high overall yield.

[Means for solving problems]

In order to achieve the above object, the present inventors have made detailed studies on the production route and physical properties of by-products produced during the production of MVL and MPD.
Various compounds produced by the reaction of PD and MVL, which are decomposed into MPD and MVL again by heating, and the reaction of MPD and MVL to form a high boiling point compound, and the MPD and MVL of the compound. Focusing on the fact that the decomposition reaction to give a constant equilibrium composition depending on the reaction conditions,
The present invention has been completed. That is, the present invention uses an oxide composed of at least one metal selected from copper, chromium and zinc in a non-oxidizing gas atmosphere under MHP.
When producing MVL and MPD by reacting
In the method for producing MVL and MPD, the residual liquid obtained by distilling MVL and MPD from the reaction mixture is circulated in the reaction system.

In the present invention, it is necessary to circulate in the reaction system the residual liquid containing the high boiling point compound obtained by distilling MVL and MPD from the reaction mixture by a known means such as distillation. Usually, when the high boiling point compound is reacted without being circulated, about 5 to 30% by weight of a high boiling point by-product is produced, but after the MVL and MPD are distilled off, the high boiling point compound produced by the reaction is reacted. When it is circulated in the system, no further accumulation of high-boiling compounds is observed in the subsequent reactions, and the concentration of high-boiling compounds is always kept in the reaction system at a constant value depending on the reaction conditions. The high boiling point compound to be circulated in the present invention can be the one produced in the same reactor as it is, but it does not matter even if it is synthesized in another reactor and added to the reaction system to start the reaction. . In this case, even if a high-boiling-point compound in an amount larger than the equilibrium amount produced in the reaction system is added, the high-boiling-point compound in an equilibrium amount or more is decomposed into MVL and MPD, and there is no particular problem. As described above, in the present invention, the high-boiling compound has a constant equilibrium composition with MVL and MPD, so that when the reaction reaches a steady state, the high-boiling compound is apparently no longer produced, and the high-boiling compound is not added to the feed material MHP. High overall yield MVL
And MPD can be produced. The total yield here means the total yield of MVL and MPD. Conventionally, it has been common to circulate high boiling components, including catalysts, in the reaction system in homogeneous catalytic reactions, etc., but in general reactions for the purpose of recycling and reuse of the catalyst, the reaction results are improved. Rather, as the circulation number increases, the accumulation of high-boiling by-products is added every time, and the reaction performance itself tends to gradually decrease. However,
In the present invention, the circulation of the catalyst is essentially unnecessary, and the effect peculiar to the reaction system of the present invention, which is completely different from the conventional one, is recognized. Although the reaction of the present invention is a reaction involving a remarkably large side reaction, regardless of the presence or absence of the circulation of the catalyst, the circulation of the high-boiling compound is positively performed to form a high-boiling compound. It is quite surprising that the reaction is suppressed, the reaction performance is improved, and a high combined yield of MVL and MPD is achieved.

Further, when the catalyst is reacted in a suspended state in the present invention, the catalyst can be circulated at the same time as the high boiling point compound, which is industrially preferable. Needless to say, when a part of the high boiling point compound is extracted for the purpose of renewing the deactivated catalyst, the formation of the high boiling point compound commensurate with the extracted amount is recognized only in the reaction immediately thereafter.

The reaction according to the method of the present invention is carried out under an atmosphere of non-oxidizing gas in order to avoid oxidation of the reaction raw materials and products. Nitrogen is a typical example of a preferable non-oxidizing gas,
Inert gases such as helium, argon and hydrogen gas may be mentioned. As these non-oxidizing gases, only one kind of gas may be used, or two or more kinds of gas may be mixed and used. Among them, it is preferable to use nitrogen gas or hydrogen gas from the industrial viewpoint.

In the method of the present invention, when the reaction is carried out in an atmosphere of nitrogen gas, the production ratio of MVL and MPD can be carried out at a ratio of 1/1 or more. The ratio can be implemented at a ratio of less than 1/1.

The reaction according to the method of the present invention is
It is preferable to carry out the treatment at a pressure of 50 absolute atmospheric pressure or less, since the yield of the above tends to be low. The reaction can also be carried out under reduced pressure, but it is more preferable to carry out the reaction within the range of 0.01 to 20 absolute atmospheric pressure in order to isolate MVL and MPD without substantial loss.

In the reaction according to the method of the present invention, if the temperature is too low, the reaction rate tends to be low, and if it is too high, the yield of MPD tends to be low, and therefore the temperature is preferably 110 to 190 ° C.
(More preferably 130 to 180 ° C.).

In the reaction according to the method of the present invention, an oxide composed of at least one metal selected from copper, chromium and zinc is used. Specific examples of such oxides include copper chromium oxide, copper zinc oxide, and copper chromium zinc oxide. These metal oxides can be used alone, but can also be used by supporting them on a carrier such as alumina, silica, or diatomaceous earth. The metal oxides are tungsten, molybdenum, rhenium, zirconium, manganese, titanium, iron, barium, magnesium,
It may be partially modified with another metal selected from calcium or the like or a compound of these metals. The metal oxide, which may be supported or partially modified, is commercially produced as a catalyst used in a reaction such as hydrogenation or dehydrogenation, and is easily available. Organic Syntheses Co
ll. Vol. II, 142 (1943), J. Am. C
hem. Soc. 54, 1138 (1932), J.
Am. Chem. Soc. , 58, 1053 (193
6), Ind. Eng. Chem. , 27, 134 (1
935), Ind. Eng. Chem. , 21, 105
2 (1929) and the like. Depending on the type of the metal oxide, the catalytic activity may be improved if it is treated with hydrogen prior to use. These metal oxides are usually used alone, but it is also possible to use two or more kinds in combination.

MHP used as starting material in the process of the invention
Can be easily obtained, for example, by hydroformylating 3-methyl-3-buten-1-ol by a known method in the presence of a rhodium complex compound with a mixed gas of hydrogen and carbon monoxide. It is possible (Japanese Patent Publication Sho 58-40
No. 533, Japanese Patent Publication No. 60-4832, and Japanese Patent Laid-Open No. 6
0-19781, etc.).

The reaction according to the method of the present invention is carried out in the liquid phase. In the present invention, it is not necessary to positively allow an organic solvent other than the reaction product to exist, but an organic solvent inert to the reaction may be used. In this case, if the amount of the organic solvent is too large, the merit of the present invention is not so remarkable, so that it is preferably used at 40% by weight or less. Specific examples of such organic solvents include liquid paraffin, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, biphenyl, diphenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ethyl, saturated aliphatic such as dioctyl phthalate. Examples thereof include hydrocarbons, saturated alicyclic hydrocarbons, aromatic hydrocarbons, ethers and esters. It goes without saying that in selecting these organic solvents, consideration should be given to the desired reaction temperature and reaction pressure and the boiling point difference between MHP, MVL and MPD and the organic solvent. Further, as described above, it is industrially advantageous to carry out the reaction in the absence of such an organic solvent, and in the present invention, the effect is particularly exerted in the absence of such an organic solvent. To be done.

The reaction according to the method of the present invention can be carried out by either a contact system of a suspension bed or a fixed bed, or a batch or continuous operation system. In order to suppress the side reaction, it is preferable to carry out the reaction so that the concentration of MHP in the reaction system does not become too high by a method such as continuously supplying MHP to the reaction system. As the reaction time or the residence time, a time range in which the conversion of MHP does not reach 100% may be selected.
A time range may be selected so that the HP conversion rate is 100%. In the reaction according to the method of the present invention, by selecting the reaction conditions such as the kind and concentration of the metal oxide, the reaction temperature, the reaction pressure, the partial pressure of hydrogen gas in the reaction atmosphere, the reaction time (or the residence time), etc. Regarding MVL and MPD, MVL / MPD (molar ratio) is usually 9/1 to 1 /
It is possible to simultaneously generate at an arbitrary ratio within the range of 9. The MVL, MPD and optionally the unreacted MHP present in the reaction mixture obtained by such a reaction can be removed by conventional separation operations, for example distillation operations, after removal of the metal oxides from the reaction mixture. Can be easily acquired separately.

In the reaction, the batch reaction can be carried out by charging only the raw material MHP, but industrially, the product is used as a reaction solvent for MHP.
Is preferably fed continuously for reaction.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

〔Example〕

Example 1 A powdered copper chromium oxide catalyst (CuO—Cr ₂ O ₃ , 0.5 wt% Mn) was placed in a 500 ml electromagnetic stirring autoclave equipped with an MHP feed port, a gas supply port, and a sampling port.
O ₂ JGC Chemical Co., Ltd. N-203) 3.0 g and MPD15
After charging 0 g and thoroughly replacing the inside of the system with hydrogen gas,
The temperature was raised to 160 ° C. with stirring while maintaining the hydrogen pressure at 10 kg / cm ² G and the off gas flow rate at 15 Nl / hr. Then MHP
150 g was fed through a quantitative feed pump for 2.5 hours. After the feed was completed, the reaction was continued for another 30 minutes to complete the reaction. Using the internal pressure from the sampling port, a small amount of the reaction mixture was withdrawn and analyzed by gas chromatography. As a result, the reaction mixture was unreacted MHP.
0.5 wt%, MVL17.0 wt%, MPD71.0
% Of high-boiling compounds and 10.5% by weight of high-boiling compounds. The conversion rate of MHP was 99 mol%,
Selectivities of L and MPD on the basis of reacted MHP were 35 mol% and 44 mol% (total selectivity of MVL and MPD was 79 mol%), respectively, and the total yield of MVL and MPD was 78 mol.

Example 1 The reaction mixture of Comparative Example 1 was treated using a wiper type thin film evaporator under reduced pressure of 140 ° C. and 10 Torr to distill about half, and 152 g of a liquid containing a catalyst, a high boiling point compound and MPD was obtained. Obtained. As a result of analyzing this liquid by gas chromatography, 77.3% by weight of MPD was detected, and the rest was a catalyst and a high boiling point compound.

The above-mentioned evaporation residual liquid containing a catalyst, a high boiling point compound and MPD was charged into the apparatus of Comparative Example 1, and MHP was performed under the same conditions as in Comparative Example 1.
150 g was reacted. After completion of the reaction, a part of the reaction mixture was sampled from the sampling port and analyzed by gas chromatography. As a result, the reaction mixture was 0.2% by weight of MHP, 20.4% by weight of MVL, 67.4% by weight of MPD and 11 of the high boiling point compound. It consisted of 0.0% by weight. MHP
Of 99.5 mol% and the selectivity of the produced MVL and MPD based on the reacted MHP was 4 respectively.
1 mol% and 58 mol% (total selectivity of MVL and MPD 99 mol%), and the overall yield of MVL and MPD was 99 mol%.

Example 2 The experiment of Example 1 was repeated 8 times. The results of the 4th and 8th reactions are shown in Table 1. It can be seen from Table 1 that almost no by-product of the high boiling point compound is observed.

Example 3 An experiment was conducted in the same manner as in Comparative Example 1 except that the metal oxides shown in Table 2 below were used and the reaction temperatures and gas atmospheres shown in Table 2 were adopted, and the same treatment as in Example 1 was performed. The reaction was carried out by circulating a high boiling by-product. The results of the second reaction obtained are shown in Table 2.

Example 8 After the completion of the reaction in Comparative Example 1, the catalyst was removed from the reaction mixture with a glass filter. The liquid was treated at 7 Torr and 120 to 140 ° C. using a vacuum distillation apparatus to distill about half, and a residual liquid 147 containing MPD and a high boiling point compound.
g was obtained. As a result of analyzing this liquid by gas chromatography, MPD was 78.5% by weight, and the rest was a high boiling point compound. Copper chrome oxide catalyst (N
-203) 3.0 g and evaporation residual liquid 150 g were charged,
Under the same conditions as in Comparative Example 1, 150 g of MHP was reacted. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and as a result, the reaction mixture was found to have MHP of 0.5% by weight and MVL2.
It consisted of 0.8% by weight, 66.8% by weight of MPD and 10.9% by weight of high-boiling compounds. From these results M
The conversion of HP was 99 mol%, and the selectivity of the produced MVL and MPD on the basis of the reacted MHP was 4 respectively.
2 mol% and 57 mol% (total selectivity of MVL and MPD 99 mol%), and the overall yield of MVL and MPD was 98 mol%.

〔The invention's effect〕

According to the method of the present invention, a compound useful as a raw material of polyurethane, a raw material which can be derived into a polymer compound useful as a modifier for a coating material or a modifier for a resin, and as an intermediate for medicines, agricultural chemicals, perfumes, etc. It is possible to obtain MVL as a raw material, MPD as a raw material for polyester, polyurethane and the like with high productivity and high yield, and the utility of the present invention is extremely large.

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Claims (1)

[Claims] 1. β-Methyl by reacting 2-hydroxy-4-methyltetrahydropyran in an atmosphere of a non-oxidizing gas using an oxide composed of at least one metal selected from copper, chromium and zinc. In producing -δ-valerolactone and 3-methylpentane-1,5-diol, the residue obtained by distilling β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol from the reaction mixture The liquid is circulated in the reaction system, β-methyl-δ-valerolactone and 3-methylpentane-
Process for producing 1,5-diol.