JPH0653691B2 - 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-1,5.
-Regarding a method for producing a diol (hereinafter, referred to as MPD), specifically, 2-hydroxy-4-methyltetrahydropyran (hereinafter, referred to as MHP) is reacted under specific conditions to produce MVL and MPD. MVL
And a method for manufacturing an MPD.

[Conventional technology]

Conventionally, as a method for producing MVL, a method of treating β, β-dimethylacrylic acid ethyl ester with a mixed gas of hydrogen and carbon monoxide at high temperature and high pressure in the presence of a cobalt-based catalyst (Chemische Berich).
te, Vol. 97, p. 863, issued 1964), or a method of oxidative dehydrogenation of MPD at a temperature of 200 ° C. in the presence of a copper chromium oxide catalyst (Organic Sy).
ntheses 35, page 87) and the like. In addition, as a method for producing a compound similar to MVL, B
all. Chem. Soc. Japan, 35, 986
In (1962), 2-hydroxytetrahydropyran (δ-oxyvaleraldehyde) is used as a catalyst in which copper zinc oxide, copper chromium oxide or copper chromium zinc oxide is used, and a continuous gas phase is formed at a temperature of 220 to 230 ° C. Let it react δ
-It is described that valerolactone was obtained.

On the other hand, as a method for producing MPD, a method of hydrogenating MHP in the presence of a hydrogenation catalyst at elevated temperature and elevated pressure (see Japanese Patent Publication No. 58-40333).
Have been proposed.

[Problems to be Solved by the Invention] In the above-mentioned publicly known document relating to the production of MVL or MPD, there is no report that MVL and MPD are simultaneously produced. 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 simultaneously produced by reacting them 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. 0-178928. However, in the above invention, MHP and / or MPD, which are the products, are used as a reaction solvent to react MHP to give M
It was found that in the case of producing VL and MPD, a large amount of high-boiling compounds are produced, 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 that can produce MVL and MPD in a high overall yield even in the presence of a solvent using a common raw material and a reaction product as a reaction solvent. It is to provide a manufacturing method of.

Another object of the present invention is to provide a highly productive industrially-friendly MVL and MP capable of producing MVL and MPD in a high overall yield under relatively mild operating conditions.
It is to provide a manufacturing method of D.

[Means for solving problems]

The present inventors have earnestly studied to achieve the above-mentioned object, and arrived at the present invention. That is, according to the present invention, MHP and MPD are produced by reacting MHP in an atmosphere of a non-oxidizing gas using an oxide composed of at least one metal selected from copper, chromium and zinc. To the general formula The method for producing MVL and MPD is characterized by carrying out the reaction in the presence of a compound represented by

In the present invention, when MHP is reacted with at least one metal oxide selected from copper, chromium and zinc in a non-oxidizing gas atmosphere, the compound represented by the above general formula (I) is added. It must be present in the reaction system. (I)
In the formula, m and n are not 0 at the same time 1 ≦ m + n ≦
It is a number that satisfies 30. If m + n is out of this range, it is not practical. Among them, a compound satisfying 1 ≦ m + n ≦ 10 in which m and n do not become 0 at the same time is preferable from a practical viewpoint, and particularly 1 ≦ m and n do not become 0 at the same time.
A compound satisfying m + n ≦ 4 is more practical and is preferably used.

The compound represented by the general formula (I) can be easily obtained by a known method, for example, the method disclosed in JP-A-60-55026, and is synthesized in the reaction system of this reaction. You may use the thing.

If the amount of the compound represented by the general formula (I) is too small, the effect of addition is small, and if it is too large, the effect tends not to increase so much relative to the amount of addition, so that it is usually 2 to the reaction mixture. It is desirable to carry out at 20% by weight (preferably 5 to 15% by weight). The total yield referred to in the present invention is M
It means the total yield of VL and MPD.

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,
Intangible gases such as helium, argon and hydrogen gas can 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. A production ratio of less than 1/1 is possible.

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, an organic solvent other than the reaction product need not be positively present, 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 an organic solvent include liquid paraffin, hexane, heptane,
Saturated aliphatic hydrocarbons such as octane, cyclohexane, benzene, toluene, xylene, biphenyl, diphenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ethyl, dioctyl phthalate, saturated alicyclic hydrocarbons, aromatic hydrocarbons, ethers and Examples thereof include 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.

The reaction is carried out in the presence of the compound represented by the general formula (I) in the starting material MH.
The batch reaction can be carried out by charging only P, but industrially it is preferable to carry out the reaction by continuously feeding MHP using the product as the reaction solvent.

〔Example〕

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

Example 1 According to the method described in JP-A-60-55026,
A MVL ring-opening polymer represented by m + n = 2 in the general formula (I) was synthesized, and MHP was synthesized according to a known method.

A 500 ml electromagnetic stirrer autoclave equipped with an MHP supply port, a gas supply port, a gas discharge port, and a reaction solution sampling port was added to a powdery (200 mesh) copper chrome oxide catalyst (CuO-Cr ₂ O ₃ , 0). 3.0% of 0.5% MnO ₂ manufactured by JGC Chemical Co., Ltd., 45 g of the ring-opening polymer and MP
D105 g was charged, the inside of the system was sufficiently replaced with hydrogen gas, and the temperature was raised to 150 ° C. with stirring while maintaining the pressure at 9 kg / cm ² G and the release gas rate at 15 Nl / hr.

Then, 150 g of MHP was fed by a pressure metering pump for 2.5 hours. After the feed was completed, stirring was continued for another 30 minutes at a temperature of 150 ° C. A small amount of the reaction liquid was extracted from the sampling port using the internal pressure and analyzed by gas chromatography.
0.2 wt%, MVL 19.2 wt% and MPD6
It consisted of 5.7% by weight. The conversion rate of MHP is 99.
6%, and the selectivities of MVL and MPD are 38.
4 mol% and 61.4 mol%, MVL and M
The overall yield of PD was 99 mol%.

Examples 2 to 6 and Comparative Example 1 Using the metal oxides shown in Table 1, n + m = 1.5
The reaction was carried out in the same manner as in Example 1 except that the MVL ring-opening polymer represented by and the MPD were used in the weights shown in Table 1 and the reaction temperatures shown in Table 1 were adopted. The results obtained are shown in Table 1.

Example 7 Using the same apparatus as in Example 1 and using as a reaction solvent However, 25 g of MVL ring-opening polymer represented by n + m = 16.5 and 125 g of MVL were charged, and the reaction pressure was adjusted to 1
A reaction was prepared in the same manner as in Example 1 except that the reaction temperature was 6 kg / cm ² (gauge pressure) and the reaction temperature was 160 ° C.

The reaction mixture is MHP 0.1% by weight, MVL 56% by weight,
And 36% by weight of MPD. The conversion of MHP is 99.8%, the selectivity of MVL and MPD are 28 mol% and 72 mol% respectively, and MVL and M
The overall yield of PD was almost 100 mol%.

Example 8 In the same electromagnetic stirring autoclave as used in Example 1, 2.3 g of the same copper chromium oxide catalyst as used in Example 1, 65 g of dioctyl phthalate and n + m =
15 g of the MVL ring-opening polymer represented by 7 was charged, the inside of the system was sufficiently replaced with hydrogen gas, the pressure was 10 kg / cm ² (gauge pressure), and the release gas rate was 160 N / l while maintaining the rate of 15 Nl / hr. The temperature was raised to ° C. Then, 150 g of MHP was fed by a pressure metering pump for 1 hour. After the feed was completed, stirring was continued for another 60 minutes. After the reaction was completed, the reaction mixture was taken out from the sampling port by utilizing the internal pressure. The obtained reaction mixture was analyzed by gas chromatography to find that the conversion of MHP was 99% and that the products contained 42 mol% of MVL and MPD, respectively.
And was found to have been formed with a selectivity of 58 mol%. The total yield of MVL and MPD is 99 mol%.
It was.

Examples 9 to 12 The reaction was carried out in the same manner as in Example 8 except that the reaction pressure and reaction temperature shown in Table 2 were adopted. The results obtained are shown in Table 2.

Example 13 An electromagnetic stirring autoclave with a content of 500 ml equipped with an MHP supply port, a gas supply port, a gas exhaust port, and a distillation cooling tube was used, and a powdery (200 mesh) copper chromium oxide catalyst (CuO—Cr ₂ O) was added. ₃ , 0.5% MnO ₂ ; N manufactured by JGC Chemical Co., Ltd.
-203) 3.0 g, 36 g of MVL ring-opening polymer represented by n + m = 3 and 114 g of MPD were charged, the inside of the system was sufficiently replaced with hydrogen gas, the pressure was 9 kg / cm ² (gauge pressure), and the outflow gas velocity. Was maintained at 15 Nl / hr and the temperature was raised to 150 ° C. with stirring. Then, 150 g of MHP was fed by a pressure metering pump for 4 hours. After finishing the feed, continue stirring at a temperature of 150 ° C. for another hour,
Hydrogen gas was discharged, and distillation was performed under a reduced pressure of 15 to 20 mmHg by a vacuum pump to distill 149 g at 140 to 155 ° C. When the distillate was analyzed by gas chromatography, it was found that the distillate had MHP of 0.8% by weight and MVL29 of
% And 70% by weight MPD. next,
After the hydrogen pressure was increased again to 9 kg / cm ² (gauge pressure), the reaction and distillation were carried out in the same manner as the first time to obtain 150 g of distillate. Gas chromatographic analysis revealed that the distillate had MHP of 0.7% by weight and MVL of 35% by weight.
And 64% by weight of MPD.

Next, the same reaction and distillation operation as the first and second times were repeated 5 times in total. Table 3 shows the amount of distillate and the composition thereof at each time.

The effects of the present invention are clear from the above examples and comparative examples.

〔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.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B01J 23/72 X 8017-4G 23/80 X 8017-4G 23/86 X 8017-4G 31/02 X 7821- 4G C07B 61/00 300

Claims (7)

[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 the production of -δ-valerolactone and 3-methylpentane-1,5-diol, the general formula was used in the reaction system. (In the formula, m and n are not 0 at the same time. 1 ≦ m + n
A method of producing β-methyl-δ-valerolactone and 3-methylpentane-1,5-diol, wherein the reaction is carried out in the presence of a compound represented by ≦ 30). 2. The production method according to claim 1, wherein m and n in the general formula (I) are numbers satisfying 1 ≦ m + n ≦ 10 which do not become 0 at the same time. 3. The method according to claim 1, wherein m and n in the general formula (I) are numbers satisfying 1 ≦ m + n ≦ 4 which do not become 0 at the same time. 4. The production method according to claim 1, wherein the reaction pressure is 50 absolute pressure or less. 5. The production method according to any one of claims 1 to 3, wherein the pressure of the reaction is 0.01 to 20 absolute atmospheric pressure. 6. The method according to any one of claims 1 to 5, wherein the reaction temperature is 110 to 190 ° C. 7. The method according to any one of claims 1 to 5, wherein the reaction temperature is 130 to 180 ° C.