阅读说明：本技术 环丁二醇骨架化合物的制造方法 (Method for producing cyclobutanediol skeleton compound ) 是由 古里伸一 川邉俊行 鹤冈香织 佐治木弘尚 山田强 朴贵焕 于 2021-03-19 设计创作，主要内容包括：本发明提供一种能够稳定地取得顺式：反式比高的环丁二醇骨架化合物的制造方法。通过将选自环丁二酮骨架化合物、环丁烷酮醇骨架化合物及环丁二醇骨架化合物的群组中的至少一种化合物作为原料,在金属催化剂存在下,不添加溶媒而在固相状态下进行催化氢化反应及环丁二醇骨架化合物中的异构化反应,制造环丁二醇骨架化合物的顺式：反式比为1.5：1～5000：1的环丁二醇骨架化合物。(The present invention provides a method for stably obtaining a cis: a process for producing a cyclobutanediol skeleton compound having a high trans ratio. A cis-form of a cyclobutanediol skeleton compound is produced by using at least one compound selected from the group consisting of a cyclobutanedione skeleton compound, a cyclobutanediol skeleton compound and a cyclobutanediol skeleton compound as a raw material, and performing a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol skeleton compound in a solid phase state in the presence of a metal catalyst without adding a solvent, wherein the starting material is selected from the group consisting of: trans ratio 1.5: 1-5000: 1 is a cyclobutanediol skeleton compound.)

1. A process for producing a cyclobutanediol skeleton compound, which comprises subjecting at least one compound selected from the group consisting of a cyclobutanediol skeleton compound, a cyclobutanediol skeleton compound and a cyclobutanediol skeleton compound as a starting material to a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol skeleton compound in a solid phase state in the presence of a metal catalyst without adding a solvent, thereby producing a cis-form of the cyclobutanediol skeleton compound: trans ratio 1.5: 1-5000: 1 is a cyclobutanediol skeleton compound.

2. The method for producing a cyclobutanediol skeleton compound according to claim 1, wherein said cyclobutanedione skeleton compound is a cyclobutanedione skeleton compound represented by general formula (1);

here, R¹、R²、R³And R⁴Independently hydrogen, C1-20 alkyl, C1-20 halogenated alkyl, C3-20 cycloalkyl or C4-30 aryl, R¹、R²、R³And R⁴Can be mutually bondedThereby forming a ring structure.

3. The method for producing a cyclobutanediol skeleton compound according to claim 1, wherein said metal catalyst is a catalyst containing at least one metal selected from the group consisting of Ru, Pt, Pd, Rh, Ni and Cu.

4. The method for producing a cyclobutanediol skeleton compound according to claim 1, wherein said metal catalyst is a catalyst containing Ru.

5. The method for producing a cyclobutanediol skeleton compound according to claim 1, wherein said support of said metal catalyst is activated carbon, alumina, silica, ceramic or cellulose.

6. The process for producing a cyclobutanediol skeleton compound according to claim 1, wherein the partial pressure of hydrogen in the reaction is in the range of 0.02MPa to 50MPa, and the reaction temperature is in the range of 10 ℃ to 150 ℃.

Technical Field

The present invention relates to a method for producing a cyclobutanediol skeleton compound.

Background

Cyclobutanediol backbone compounds, represented by 2,2,4, 4-tetramethylcyclobutane-1, 3-diol (hereinafter TMCBD) can be used in the manufacture of various polymer materials, for example, polyesters derived from dicarboxylic acids and TMCBD have high glass transition temperatures and excellent weatherability and hydrolytic stability when compared to similar polyesters made from other commonly used polyester forming diols.

The stereoisomers of the hydroxyl group of TMCBD include cis-isomer and trans-isomer, and the cis-form of TMCBD is obtained by catalytic hydrogenation (catalytic hydrogenation) of 2,2,4, 4-tetramethylcyclobutane-1, 3-dione (hereinafter, tmcbk (tetramethylcyclohydrogenation)): the trans ratio may be between about 1: 1 to about 1.5: 1, in the presence of a catalyst. The cis form is known: the trans ratio affects important properties of polyesters with TMCBD, the cis: the stable control of the trans ratio is important because it is stable in the quality of the polyester.

As cis-regulating TMCBD: the trans-ratio method has been reported only as isomerization, that is, isomerization in which no substantial TMCBD is produced. Reacting the cis: trans ratio of 0: 1-1.5: 1 to cis: trans ratios of different products. However, since the method is isomerization in a state of being completely dissolved in a solvent, even if cis: the trans ratio is high and can only rise to about 1.5: 1 (patent document 1).

In addition, in catalytic hydrogenation from TMCBK to TMCBD, there is a reported example in which hydrogenation is performed at a reaction temperature higher than the dew point of TMCBD in the gas phase. However, in the present method, the cis: trans ratio of about 1: 1 to about 1.6: 1, which is not very different from the complete dissolution system, and requires 100 to 500mol of hydrogen, etc., and is inefficient as a production process (patent document 2).

Further, as a method for improving the cis form of TMCBD: as a method of trans-ratio, there is a report example using reaction crystallization in which a cis-isomer is precipitated during the reaction. The present method is a method of bringing TMCBK into contact with hydrogen in the presence of a ruthenium catalyst using water, a hydrocarbon or a mixture thereof as a solvent, thereby precipitating cis (cis) -TMCBD formed, and as a result, obtaining cis in the reaction system: TMCBD with a high trans ratio. However, as an example, cis-TMCBD is obtained by filtering once in a state where cis-TMCBD is deposited and washing the filtered product with a solvent in which cis-TMCBD is dissolved, and as a result, the amount of solvent used increases in the steps from the reaction to the recovery of cis-TMCBD, and thus it cannot be said that the process is environmentally friendly from the viewpoint of green chemistry (patent documents 3 to 4).

On the other hand, from the viewpoint of green sustainable chemistry, there are reported examples of hydrogenation and suzuki coupling in a solid phase state in which a raw material, an intermediate, a product, and a catalyst are solid without using a solvent. Regarding the hydrogenation, it was confirmed that a favorable hydrogenation reaction was carried out by using an unsaturated hydrocarbon, an azide derivative, benzyl ether or the like in the presence of a palladium catalyst under conditions in which the partial pressure of hydrogen is atmospheric pressure (non-patent document 1).

Heretofore, a method of reducing a cyclobutanedione skeleton compound such as TMCBK with a ruthenium catalyst in a solid phase state without using a solvent has not been studied. There is a need for the development of a process for producing a cyclobutanediol skeleton compound such as TMCBD which is environmentally compatible from the viewpoint of green chemistry, and there is a need for the development of a cyclobutanediol skeleton compound which can stably obtain the cis-form: a process for preparing cyclobutanediol skeleton compounds with high trans ratio.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/078439

Patent document 2: international publication No. 2012/078384

Patent document 3: international publication No. 2016/094478

Patent document 4: international publication No. 2016/094479

Non-patent document

Non-patent document 1: tetrahedron 67(2011)8628-8634

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of developing a process for producing a cyclobutanediol skeleton compound that is environmentally compatible from the viewpoint of green chemistry, and that can stably obtain the cis-form: a cyclobutanediol skeleton compound with high trans ratio.

Means for solving the problems

The present inventors have found that a cis-form can be stably obtained by reacting or isomerizing a cyclobutanediol skeleton compound in a solid phase state in the presence of a metal catalyst without using a solvent in the catalytic hydrogenation of the cyclobutanedione skeleton compound to the cyclobutanediol skeleton compound or in the cis-trans isomerization of the cyclobutanediol skeleton compound: a cyclobutanediol skeleton compound with high trans ratio.

The present invention has been completed based on the above-described findings.

Namely, the present invention is as follows.

[1] A process for producing a cyclobutanediol skeleton compound, which comprises subjecting at least one compound selected from the group consisting of a cyclobutanediol skeleton compound, a cyclobutanediol skeleton compound and a cyclobutanediol skeleton compound as a starting material to a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol skeleton compound in a solid phase state in the presence of a metal catalyst without adding a solvent, thereby producing a cis-form of the cyclobutanediol skeleton compound: trans ratio 1.5: 1-5000: 1 is a cyclobutanediol skeleton compound.

[2] The method for producing a cyclobutanediol skeleton compound according to item [1], wherein said cyclobutanediol skeleton compound is a cyclobutanedione skeleton compound represented by general formula (1);

here, R¹、R²、R³And R⁴Independently hydrogen, C1-20 alkyl, C1-20 halogenated alkyl, C3-20 cycloalkyl or C4-30 aryl, R¹、R²、R³And R⁴May be bonded to each other to form a ring structure.

[3] The process for producing a cyclobutanediol skeleton compound according to item [1] or item [2], wherein said metal catalyst is a catalyst containing at least one metal selected from the group consisting of Ru, Pt, Pd, Rh, Ni and Cu.

[4] The process for producing a cyclobutanediol skeleton compound according to any one of the items [1] to [3], wherein said metal catalyst is a catalyst containing Ru.

[5] The process for producing a cyclobutanediol skeleton compound according to any one of items [1] to [4], wherein the carrier of said metal catalyst is activated carbon, alumina, silica, ceramic or cellulose.

[6] The process for producing a cyclobutanediol skeleton compound according to any one of the items [1] to [5], wherein the partial pressure of hydrogen in the reaction is in the range of 0.02MPa to 50MPa, and the reaction temperature is in the range of 10 ℃ to 150 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

The method for producing a cyclobutanediol skeleton compound of the present invention can obtain a cyclobutanediol skeleton compound having a higher cis-isomer ratio than conventional ones under mild reaction conditions, and can be said to be a process which is environmentally friendly in terms of green chemistry, without using a reaction solvent.

Detailed Description

Embodiments of the present invention will be explained. The present invention is not limited to the following embodiments.

The method for producing a cyclobutanediol skeleton compound of the present invention is characterized in that: by carrying out the catalytic hydrogenation reaction and the isomerization reaction in the cyclobutanediol skeleton compound in a solid phase state without adding a solvent to the raw material and the metal catalyst, the cyclobutanediol skeleton compound has a cis-form: the trans ratio becomes high.

The raw material may use at least one compound selected from the group of cyclobutane ketone skeleton compounds, cyclobutane alkanol skeleton compounds and cyclobutane diol skeleton compounds without particular limitation.

For example, the cyclic butanedione skeleton compound is a cyclic butanedione skeleton compound represented by general formula (1).

Here, R¹、R²、R³And R⁴Independently hydrogen, C1-20 alkyl, C1-20 halogenated alkyl, C3-20 cycloalkyl or C4-30 aryl, R¹、R²、R³And R⁴May be bonded to each other to form a ring structure.

The metal of the metal catalyst is at least one metal selected from the group consisting of Ru, Pt, Pd, Rh, Ni and Cu. Preferably Ru.

The carrier of the metal catalyst is at least one carrier selected from activated carbon, graphite, graphene oxide, alumina, silica, titanium dioxide, ceramic, cellulose and hydroxyapatite. Carbon and alumina are preferred.

The metal loading of the metal catalyst is 0.1 to 15 wt%, preferably 0.2 to 10 wt%.

The metal catalyst may be in a dry state or in a wet state with water or the like. The amount of water in a wet state is 1 to 200% by weight, preferably 5 to 100% by weight.

The catalyst concentration may vary over a wide range, but is adjusted within a range of 0.001 mol% to 50 mol% (molar (mol) amount of the catalyst metal relative to the molar amount of the raw material), preferably 0.01 mol% to 20 mol%, more preferably 0.1 mol% to 10 mol%.

In the embodiment of the present invention, the raw materials and the metal catalyst are charged into a reaction apparatus, hydrogen is introduced by substitution in a solid phase state without adding a solvent, and the reaction is carried out under a predetermined reaction temperature and mixing conditions.

The reaction apparatus may be any container capable of replacing a gas, and a flask, an autoclave, or the like may be used. Further, a rotary evaporator in which the vessel itself is rotated and which can be mixed inside may be used, or a method of supplying hydrogen to a column-type fixed bed or the like in which the raw material and the catalyst are mixed and filled in advance may be used. Further, a fluidized bed type reactor capable of semi-continuously treating solids, a Nauta mixer (Nauta-mixer), a ribbon blender, an "SV mixer" manufactured by kobelco eco-solutions gmbh, and a "PV mixer" manufactured by kobelco environmental solutions, ltd, may also be used.

The raw material and the metal catalyst may be charged separately or in a state of being mixed in advance. In order to suppress a sudden load of the stirring power of the reactor, the reactor may be charged with the stirring operation of the reactor.

As a method of hydrogen replacement in the reactor, there is a method of introducing a large amount of hydrogen for replacement; a method of repeatedly pressurizing and purging with hydrogen or an inert gas; and a method of repeatedly introducing hydrogen after reducing the pressure in the reactor. In the embodiment of the present invention, since the solid phase state is obtained without adding a solvent, there is no fear of evaporation of the solvent, and the like, and therefore, a method of repeatedly introducing hydrogen after reducing the pressure in the reactor is preferable.

The hydrogen in the reactor may be in a mixed state with an inert gas, and the hydrogen partial pressure may be in the range of 0.02MPa to 50MPa, preferably 0.05MPa to 5MPa, and more preferably 0.08MPa to 0.98 MPa.

The reaction temperature is in the range of 10 ℃ to 150 ℃, preferably 30 ℃ to 100 ℃, and more preferably 50 ℃ to 80 ℃.

The mixing conditions may be such that the raw material and the metal catalyst are sufficiently mixed. When the reaction mixture is charged in a premixed state, the reaction mixture may not be particularly mixed in the reactor.

The catalyst is dissolved in a solvent after the reaction to make it non-homogeneous and can be easily removed from the reaction mixture by separation by filtration. The catalyst may be repeatedly used in the catalytic hydrogenation reaction and the isomerization reaction without further treatment, or may be repeatedly used in a wet state with water or the like used first.

The reaction mixture may be dissolved in at least one solvent selected from the group consisting of water, alcohols, ethers, hydrocarbons, ketones, and esters. Examples thereof include: water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-ethylhexanol, diethyl ether, diisopropyl ether, tetrahydrofuran, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl isobutyrate, and mixtures thereof. From the viewpoint of ease of acquisition or operability, water, methanol, 2-propanol, acetone, ethyl acetate are preferable.

[ examples ]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[ example 1]

(examples of hydrogenation at atmospheric pressure)

The reaction apparatus used was a personal organic synthesis apparatus manufactured by Tokyo Likeke instruments Ltd, Kammisidean (ChemiState)^TMPPM-5512 type.

7.14mmol of TMCBK as a raw material and 1.5g of 5 wt% Ru/C (manufactured by Fuji film and Wako pure chemical industries, Ltd.) as a catalyst (the ruthenium content in the catalyst Ru/C is 1/10mol of the raw material) were put into a 120mL test tube. After degassing the inside of the test tube, a hydrogen balloon was attached, and after replacement in a hydrogen atmosphere, the reaction temperature was set to 60 ℃ and stirred at a stirring speed of 300rpm for 6 hours to effect reaction.

(post-treatment after reaction)

Then, to the obtained reaction product, 40mL of ethyl acetate was added, and the raw material, the product, and the like were dissolved and filtered using a membrane filter (manufactured by adantatec, Dethamideke (DISMIC) (registered trademark), 13HP020AN, pore diameter 0.20 μm), thereby obtaining a reaction filtrate from which the catalyst Ru/C was removed. The catalyst Ru/C used in the reaction was washed with another 10mL of ethyl acetate, and the washing solution was collected. The cleaning solution and the reaction filtrate obtained above were combined and measured by gas chromatography (manufactured by shimadzu corporation), whereby the ratio of the raw material to the reaction product was calculated. The reaction product includes TMCBK as a raw material, TMCBK as a reductant, cis-TMCBD as a cis-isomer in a reductant, trans-TMCBD as a trans-isomer, and other substances as by-products of ring opening of the cyclobutane skeleton, and the composition of Gas Chromatography (GC) is shown in the following table. The ratio of cis-form to trans-form of TMCBD is also shown in the table.

[ examples 2 to 3]

The reaction was carried out in the same manner as in example 1 except that the reaction temperature was changed to 70 ℃ and 80 ℃.

[ examples 4 to 6]

Except that the catalyst of example 1 was changed to 5 wt% Ru/Al₂O₃(Fuji film and Wako pure chemical industries, Ltd.), and the reaction temperature is 60 degrees, 70 degrees, 80 degrees, respectively, in the same way as the embodiment 1 implementation.

The results of examples 1 to 6 are shown in table 1 below.

TABLE 1

From the results of examples 1 to 6, it is understood that TMCBD can be quantitatively obtained from TMCBK by performing the catalytic hydrogenation reaction in a solid phase state without adding a solvent, and the cis-ratio in TMCBD is high from about 4 to about 30.

[ example 7]

(examples of hydrogenation under pressure)

The reaction apparatus used was a personal organic synthesis apparatus manufactured by Tokyo Likeke instruments Ltd, Kammisidean (ChemiState)^TMPPV-4460 type ".

1.96mmol of TMCBK as a raw material and 0.13g (the content of ruthenium in the catalyst Ru/C is 1/60mol amount of the raw material) of Ru/C (A type/N.E Camkat (manufactured by A-type/N.E CHEMCAT)) having a water content of 5 wt% as a catalyst were charged into a 42mL reaction tube. Then, a gas line was connected, and after replacement in a hydrogen atmosphere, the partial pressure of hydrogen was set to 0.8MPa, the reaction temperature was set to 50 ℃, and the mixture was stirred at a stirring speed of 600rpm for 4 hours to effect reaction.

The post-treatment after the reaction was carried out in the same manner as in example 1.

[ examples 8 to 10]

The reaction was carried out in the same manner as in example 7 except that the reaction temperature was changed to 60 ℃, 70 ℃ and 80 ℃.

Comparative example 1

(examples of hydrogenation under pressure in methanol)

The reaction apparatus used was a personal organic synthesis apparatus manufactured by Tokyo Likeke instruments Ltd, Kammisidean (ChemiState)^TMPPV-4460 type ".

7.82mmol of TMCBK as a raw material, 0.53g of 50 wt% aqueous 5 wt% Ru/C (A type/N.E Camkat (A-type/N.E CHEMCAT)) as a catalyst (the ruthenium content in the catalyst Ru/C is 1/60mol amount of the raw material), and 40mL of methanol as a reaction solvent were put into a 190mL reaction tube. Then, a gas line was connected, and after replacement in a hydrogen atmosphere, the partial pressure of hydrogen was set to 0.8MPa, the reaction temperature was set to 80 ℃, and the mixture was stirred at 600rpm for 4 hours to effect reaction.

Then, the obtained reaction solution was filtered through a membrane filter (dispic (registered trademark), 13HP020AN, pore size 0.20 μm, manufactured by adantatec corporation, edomako), to obtain a reaction filtrate from which the catalyst Ru/C was removed. The subsequent operations were carried out in the same manner as in example 1.

Comparative examples 2 to 3

The reaction was carried out in the same manner as in comparative example 1 except that the reaction solvent was changed to isopropyl alcohol and ethyl acetate, respectively.

The results of examples 7 to 10 and comparative examples 1 to 3 are shown in table 2 below.

TABLE 2

From the comparison between examples 7 to 10 and comparative examples 1 to 3, it is understood that the cis ratio in TMCBD is increased by performing the catalytic hydrogenation reaction in a solid phase state without adding a solvent.

[ example 11]

(example of isomerization under pressure Using Ru/C)

The reaction apparatus used was a personal organic synthesis apparatus manufactured by Tokyo Likeke instruments Ltd, Kammisidean (ChemiState)^TMPPV-4460 type ".

1.96mmol of TMCBD before isomerization and 0.13g (the ruthenium content in the catalyst Ru/C is 1/60mol amount of TMCBD before isomerization) of Ru/C (A type/N.E Camkat (A-type/N.E CHEMCAT)) containing 50 wt% of water as a catalyst were put into a 42mL reaction tube. Then, a gas line was connected, and after replacement in a hydrogen atmosphere, the partial pressure of hydrogen was set to 0.8MPa, the reaction temperature was set to 60 ℃, and the mixture was stirred at a stirring speed of 600rpm for 5.6 hours to effect reaction.

The post-treatment after the reaction was carried out in the same manner as in example 1.

[ example 12]

(by using Ru/Al)₂O₃Examples of isomerization under pressure)

Except that the catalyst of example 10 was changed to 5 wt% Ru/Al₂O₃(Fuji film and Wako pure chemical industries, Ltd.), the same procedure was carried out.

The composition of TMCBD before isomerization and the results of examples 11 to 12 are shown in table 3 below.

TABLE 3

From the results of examples 10 and 11, it is understood that the cis-ratio of TMCBD is increased by carrying out the isomerization reaction in the cyclobutanediol skeleton compound in the solid phase state without adding a solvent.

[ example 13]

(example of hydrogenation of Dispiro [5.1.5.1] tetradecane-7, 14-dione (hereinafter, DSTDK (dispiro tetradecanoation)) by Ru/C)

The reaction apparatus used was a personal organic synthesis apparatus manufactured by Tokyo Likeke instruments Ltd, Kammisidean (ChemiState)^TMPPM-5512 type.

7.13mmol of DSTDK as a raw material and 1.50g of 5 wt% Ru/C (manufactured by Fuji photo film and Wako pure chemical industries, Ltd.) as a catalyst (the ruthenium content in the catalyst Ru/C is 1/10mol based on the raw material) were put into a 120mL reaction tube. After degassing the reaction tube, a hydrogen balloon was attached, and the reaction tube was replaced with hydrogen, and then the reaction temperature was set to 70 ℃ and stirred at a stirring speed of 300rpm for 6 hours to effect a reaction.

Then, to the obtained reaction product, 40mL of ethyl acetate was added, and the raw material, the product, and the like were dissolved and filtered using a membrane filter (manufactured by adantatec, Dethamideke (DISMIC) (registered trademark), 13HP020AN, pore diameter 0.20 μm), thereby obtaining a reaction filtrate from which the catalyst Ru/C was removed. The catalyst Ru/C used in the reaction was washed with another 10mL of ethyl acetate, and the washing solution was collected. The cleaning solution and the reaction filtrate obtained above were combined and measured by gas chromatography (manufactured by shimadzu corporation), whereby the ratio of the raw material to the reaction product was calculated. The products after the reaction include the starting material DSTDK, the first reducing agent DSTDO, cis-DSTDD as a cis-isomer in the second reducing agent, trans-DSTDD as a trans-isomer, and other substances as by-products of the ring opening of the cyclobutane skeleton, and the GC composition is shown in the following table.

[ example 14]

(by using Ru/Al)₂O₃Examples of hydrogenations carried out under pressure)

Except that the catalyst of example 13 was changed to 5 wt% Ru/Al₂O₃(Fuji film and Wako pure chemical industries, Ltd.), the same procedure was carried out.

The results of examples 13 to 14 are shown in table 4 below.

TABLE 4

From the results of examples 13 and 14, it is understood that by conducting the catalytic hydrogenation reaction in a solid phase state without adding a solvent, DSTDD can be quantitatively obtained from DSTDK, and a high cis ratio of about 7 to about 155 is obtained in DSTDD.

[ industrial applicability ]

The cis-form obtained by the method for producing a cyclobutanediol skeleton compound of the present invention: the cyclobutanediol skeleton compounds having a high trans ratio can be used as a raw material for polyesters having high stability and stable quality in terms of glass transition temperature, impact strength, weather resistance and hydrolytic stability.