Method for producing cyclobutanediol compound

Abstract

Provided is a process in which a cyclobutanediol compound having a high cis:trans ratio can be stably obtained. The cyclobutanediol compound having a cis:trans ratio of 1.5:1 to 5000:1 is produced by using at least one compound selected from a group consisting of a cyclobutanedione compound, a cyclobutane ketol compound, and a cyclobutanediol compound as a raw material, and performing a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol compound in a solid phase state in the presence of a metal catalyst without adding a solvent.

Claims

1. A method for producing a cyclobutanediol compound, comprising: using at least one compound selected from a group consisting of a cyclobutanedione compound, a cyclobutane ketol compound, and a cyclobutanediol compound as a raw material; and performing a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol compound in a solid phase state in the presence of a metal catalyst without adding a solvent to produce the cyclobutanediol compound having a cis:trans ratio of 1.7:1 to 155.5:1, wherein the metal catalyst is a catalyst containing Ru, a partial pressure of hydrogen in both of the catalytic hydrogenation reaction and the isomerization reaction is in a range of 0.1 to 0.98 MPa, and a reaction temperature is in a range of 40° C. to 90° C.

2. The method for producing a cyclobutanediol compound according to claim 1, wherein the cyclobutanedione compound is a cyclobutanedione compound represented by general formula (1), ##STR00003## wherein, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen, alkyl having 1 to 20 carbon atoms, halogenated alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, or aryl having 4 to 30 carbon atoms, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be bonded to each other to form a cyclic structure.

3. The method for producing a cyclobutanediol compound according to claim 1, wherein a carrier of the metal catalyst is activated carbon, carbon, alumina, silica, ceramic, or cellulose.

4. A method for producing a cyclobutanediol compound, comprising: using at least one compound selected from a group consisting of a cyclobutane ketol compound and a cyclobutanediol compound as a raw material; and performing a catalytic hydrogenation reaction and an isomerization reaction in the cyclobutanediol compound in a solid phase state in the presence of a metal catalyst without adding a solvent to produce the cyclobutanediol compound having a cis:trans ratio of 1.7:1 to 155.5:1, wherein the metal catalyst is a catalyst containing Ru, a partial pressure of hydrogen in both of the catalytic hydrogenation reaction and the isomerization reaction is in a range of 0.1 to 0.98 MPa, and a reaction temperature is in a range of 40° C. to 90° C.

5. The method for producing a cyclobutanediol compound according to claim 4, wherein a carrier of the metal catalyst is activated carbon, carbon, alumina, silica, ceramic, or cellulose.

Description

DESCRIPTION OF THE EMBODIMENTS

(1) An embodiment according to the disclosure is described. Moreover, the disclosure is not limited to the following embodiment.

(2) A method for producing a cyclobutanediol compound of the disclosure is characterized in that by performing a catalytic hydrogenation reaction and an isomerization reaction in a cyclobutanediol compound in a solid phase state without adding a solvent to a raw material and a metal catalyst, the cis:trans ratio of the cyclobutanediol compound becomes higher than the cis:trans ratio of a cyclobutanediol compound which is obtained by performing the reactions in a solution system using a conventional method.

(3) At least one compound selected from a group consisting of a cyclobutanedione compound, a cyclobutane ketol compound, and a cyclobutanediol compound can be used as the raw material without particular limitation.

(4) For example, the cyclobutanedione compound is a cyclobutanedione compound represented by general formula (1),

(5) ##STR00002##

(6) wherein, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen, alkyl having 1 to 20 carbon atoms, halogenated alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, or aryl having 4 to 30 carbon atoms, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be bonded to each other to form a cyclic structure.

(7) The metal of the metal catalyst is at least one metal selected from Ru, Pt, Pd, Rh, Ni, and Cu. Ru is preferable.

(8) The carrier of the metal catalyst is at least one carrier selected from activated carbon, carbon, graphite, graphene, graphene oxide, alumina, silica, titania, ceramics, cellulose and hydroxyapatite. Carbon and alumina are preferable.

(9) The amount of the metal carried by the metal catalyst is 0.1 wt % to 15 wt %, preferably 0.2 wt % to 10 wt %.

(10) The metal catalyst may be in a dry state or in a state of being wetted with water or the like. The amount of water in the wetted state is 1 wt % to 200 wt %, preferably 5 wt % to 100 wt %.

(11) Although the catalyst concentration may be varied within a wide range, it is adjusted to a range of 0.001 mol % to 50 mol % (mole quantity of the catalyst metal with respect to mole quantity of the raw material), preferably 0.01 mol % to 20 mol %, and more preferably 0.1 mol % to 10 mol %.

(12) The embodiment of the disclosure is carried out under a predetermined reaction temperature and mixing condition by charging the raw material and the metal catalyst into a reactor, introducing hydrogen by substituting the inside of the rector in a solid phase state without adding a solvent.

(13) The reactor may be a container which is capable of performing gas substitution, and a flask, an autoclave, or the like can be used. In addition, a rotary evaporator that allows the container to rotate to mix the materials inside, or a method of feeding hydrogen to a column-type fixed bed in which the raw material and the catalyst are mixed and filled in advance can also be used. Furthermore, a fluidized bed reactor that can treat solids semi-continuously, a Nauta mixer, a ribbon blender, a “SV mixer” and a “PV mixer” manufactured by Kobelco Eco-Solutions Co., Ltd. can also be used.

(14) The raw material and the metal catalyst may be charged individually or may be charged in a premixed state. In order to suppress the sudden load of the stirring power of the reactor, the raw material and the metal catalyst may be charged under the operation of the stirring of the reactor.

(15) The methods for hydrogen substitution in the reactor include a method of introducing a large amount of hydrogen to substitute the inside of the reactor, a method of repeating pressurization and purging using hydrogen or an inert gas, a method of repeating the introduction of hydrogen after the inside of the reactor is depressurized, and the like. The embodiment of the disclosure is in a solid phase state without the addition of a solvent, and thus there is no concern about evaporation of the solvent. Therefore, the method of repeating the introduction of hydrogen after the inside of the reactor is depressurized is preferable.

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

(17) The reaction temperature is in a range of 10° C. to 150° C., preferably 30° C. to 100° C., and more preferably 50° C. to 80° C.

(18) As for the mixing condition, it is sufficient that the sufficiently mixed state of the raw material and the metal catalyst are maintained. When the raw material and the metal catalyst are charged in the premixed state, it is not necessary to specially mix in the reactor.

(19) After the reaction, the catalyst can be easily removed from the reaction mixture by dissolving the reaction mixture in a solvent to make it non-uniform and filtering the reaction mixture. The catalyst may be repeatedly used for the catalytic hydrogenation reaction and the isomerization reaction without further treatment, or may be repeatedly used in a state of being wetted with water or the like used first.

(20) The reaction mixture can be dissolved in at least one solvent selected from water, alcohols, ethers, hydrocarbons, ketones and esters. The solvent includes, for example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-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 acetate, isobutyl isobutyrate, and a mixture thereof. Water, methanol, 2-propanol, acetone, and ethyl acetate are preferable in terms of availability and operability.

EXAMPLE

(21) Hereinafter, the disclosure is described in more detail with reference to examples. However, the disclosure is not limited thereto.

Example 1

(22) (Example of Hydrogenation Under Atmospheric Pressure)

(23) “Personal organic synthesizer ChemiStation™ PPM-5512 type” manufactured by Tokyo Rikakikai Co., Ltd. is used as the reactor.

(24) 7.14 mmol of TMCBK being the raw material and 1.5 g of 5 wt % Ru/C (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) being the catalyst (ruthenium content in catalyst Ru/C is 1/10 mol of the raw material) are charged into a test tube of 120 mL. After degassing the inside of the test tube, a hydrogen gas balloon is attached and the inside is substituted under a hydrogen gas atmosphere, and then the reaction temperature is set to 60° C., and the reaction is carried out by stirring at a stirring speed of 300 rpm for 6 hours.

(25) (Post-Treatment after Reaction)

(26) Then, 40 mL of ethyl acetate is added to the obtained reactant to dissolve the raw material, the resultant and the like, and filtration is performed using a membrane filter (manufactured by ADVANTEC, DISMIC (registered trademark), 13HP020AN, pore diameter 0.20 μm) to thereby obtain a reaction filtrate from which the catalyst Ru/C has been removed. In addition, the catalyst Ru/C used in the reaction is separately cleaned by 10 mL of ethyl acetate, and the cleaning liquid is recovered. The ratio of the raw material to the reaction product is calculated by mixing the cleaning liquid with the previously obtained reaction filtrate and measuring by a gas chromatograph (manufactured by Shimadzu Corporation). Moreover, the post-reactants include TMCBK being the raw material, TMCBO being a monoreduced form, cis-TMCBD being a cis isomer of a direduced form, trans-TMCBD being a trans isomer of a direduced form, and others being by-products in which the cyclobutane skeleton is opened. The gas chromatography (GC) composition is shown in the table below. In addition, the ratio of cis isomer to trans isomer of TMCBD is also shown in the table.

Examples 2 to 3

(27) The same operations are carried out except that the reaction temperature of Example 1 is changed to 70° C. and 80° C., respectively.

Examples 4 to 6

(28) The same operations are carried out as in Example 1 except that the catalyst of Example 1 is changed to 5 wt % Ru/Al.sub.2O.sub.3 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and the reaction temperature is changed to 60° C., 70° C., and 80° C., respectively.

(29) The results of Examples 1 to 6 are collectively shown in Table 1 below.

(30) TABLE-US-00001 TABLE 1 Reaction GC composition [GC %] TMCBD Temperature cis- trans- cis:trans Catalyst [° C.] TMCBK TMCBO TMCBD TMCBD Others ratio Example 1 Ru/C 60 0.0 0.6 77.7 18.2 3.6 4.3:1 Example 2 70 0.2 0.6 78.8 16.8 3.7 4.7:1 Example 3 80 0.4 0.8 73.8 17.4 7.7 4.2:1 Example 4 Ru/Al.sub.2O.sub.3 60 0.2 2.3 77.4 18.1 2.0 4.3:1 Example 5 70 2.1 4.0 88.3 3.0 2.7 29.4:1  Example 6 80 0.0 3.8 80.7 7.1 8.4 11.4:1 

(31) The results of Examples 1 to 6 show 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 as high as about 4 to about 30.

Example 7

(32) (Example of Hydrogenation Under Pressurization)

(33) “Personal organic synthesizer ChemiStation™ PPV-4460 type” manufactured by Tokyo Rikakikai Co., Ltd. is used as the reactor.

(34) 1.96 mmol of TMCBK being the raw material and 0.13 g of 5 wt % Ru/C containing 50 wt % of water (A-type/manufactured by N.E. Chemcat) being the catalyst (ruthenium content in catalyst Ru/C is 1/60 mol of the raw material) are charged into a reaction tube of 42 mL. Then, after connecting a gas line and substituting under a hydrogen gas atmosphere, the partial pressure of hydrogen is set to 0.8 MPa, the reaction temperature is set to 50° C., and the reaction is carried out by stirring at a stirring speed of 600 rpm for 4 hours.

(35) The post-treatment after the reaction is carried out in the same manner as in Example 1.

Examples 8 to 10

(36) The same operations are carried out except that the reaction temperature of Example 7 is changed to 60° C., 70° C., and 80° C., respectively.

Comparative Example 1

(37) (Example of Hydrogenation Under Pressurization in Methanol)

(38) “Personal organic synthesizer ChemiStation™ PPV-4460 type” manufactured by Tokyo Rikakikai Co., Ltd. is used as the reactor.

(39) 7.82 mmol of TMCBK being the raw material, 0.53 g of 5 wt % Ru/C containing 50 wt % of water (A-type/manufactured by N.E. Chemcat) being the catalyst (ruthenium content in catalyst Ru/C is 1/60 mol of the raw material), and 40 mL of methanol being the reaction solvent are charged into a reaction tube of 190 mL. Then, after connecting the gas line and substituting under the hydrogen gas atmosphere, the partial pressure of hydrogen is set to 0.8 MPa, the reaction temperature is set to 80° C., and the reaction is carried out by stirring at a stirring speed of 600 rpm for 4 hours.

(40) Then, the obtained reaction solution is filtered using a membrane filter (manufactured by ADVANTEC, DISMIC (registered trademark), 13HP020AN, pore diameter 0.20 μm) to obtain a reaction filtrate from which the catalyst Ru/C has been removed. Subsequent operations are carried out in the same manner as in Example 1.

Comparative Examples 2 to 3

(41) The same operations are carried out except that the reaction solvent of Comparative example 1 is changed to isopropyl alcohol and ethyl acetate, respectively.

(42) The results of Examples 7 to 10 and Comparative examples 1 to 3 are collectively shown in Table 2 below.

(43) TABLE-US-00002 TABLE 2 Reaction GC composition [GC %] TMCBD temperature cis- trans- cis:trans Solvent [° C.] TMCBK TMCBO TMCBD TMCBD Others ratio Example 7 None 50 0.1 1.0 61.7 37.0 0.3 1.7:1 Example 8 None 60 0.0 0.8 78.1 20.9 0.2 3.7:1 Example 9 None 70 0.2 1.4 70.0 27.8 0.6 2.5:1 Example 10 None 80 0.0 2.0 73.2 24.0 0.8 3.1:1 Comparative MeOH 80 0.0 0.1 42.2 57.6 0.0 0.7:1 example 1 Comparative iPrOH 80 0.0 0.1 59.8 39.9 0.2 1.5:1 example 2 Comparative AcOEt 80 0.0 0.1 50.8 48.7 0.4 1.0:1 example 3

(44) The comparison between Examples 7 to 10 and Comparative examples 1 to 3 shows 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

(45) (Example of Isomerization Under Pressurization by Ru/C)

(46) “Personal organic synthesizer ChemiStation™ PPV-4460 type” manufactured by Tokyo Rikakikai Co., Ltd. is used as the reactor.

(47) 1.96 mmol of TMCBD before isomerization and 0.13 g of 5 wt % Ru/C containing 50 wt % of water (A-type/manufactured by N.E. Chemcat) being the catalyst (ruthenium content in catalyst Ru/C is 1/60 mol of TMCBD before isomerization) are charged into a reaction tube of 42 mL. Then, after connecting the gas line and substituting under the hydrogen gas atmosphere, the partial pressure of hydrogen is set to 0.8 MPa, the reaction temperature is set to 60° C., and the reaction is carried out by stirring at a stirring speed of 600 rpm for 5.6 hours.

(48) The post-treatment after the reaction is carried out in the same manner as in Example 1.

Example 12

(49) (Example of Isomerization Under Pressurization by Ru/Al.sub.2O.sub.3)

(50) The same operations are carried out except that the catalyst of Example 10 is changed to 5 wt % Ru/Al.sub.2O.sub.3 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).

(51) The TMCBD composition before isomerization and the results of Examples 11 to 12 are shown in Table 3 below.

(52) TABLE-US-00003 TABLE 3 GC composition [GC %] TMCBD cis- trans- cis:trans Catalyst TMCBK TMCBO TMCBD TMCBD Others ratio Before 0.0 0.1 60.7 37.4 1.7 1.6:1 isomerization Example Ru/C 0.0 0.0 67.3 31.3 1.3 2.2:1 11 containing 50 wt % of water Example Ru/Al.sub.2O.sub.3 0.0 0.08 77.5 21.0 1.4 3.7:1 12

(53) The results of Examples 10 and 11 show that the cis ratio of TMCBD is increased by performing the isomerization reaction in the cyclobutanediol compound in a solid phase state without adding a solvent.

Example 13

(54) (Example of Hydrogenation of Dispiro [5.1.5.1] Tetradecane-7,14-Dione (Hereinafter, Referred to as DSTDK) by Ru/C)

(55) “Personal organic synthesizer ChemiStation™ PPM-5512 type” manufactured by Tokyo Rikakikai Co., Ltd. is used as the reactor.

(56) 7.13 mmol of DSTDK being the raw material and 1.50 g of 5 wt % Ru/C (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) being the catalyst (ruthenium content in catalyst Ru/C is 1/10 mol of the raw material) are charged into a reaction tube of 120 mL. After degassing the inside of the reaction tube, the hydrogen gas balloon is attached and the inside is substituted under the hydrogen gas atmosphere, then the reaction temperature is set to 70° C., and the reaction is carried out by stirring at a stirring speed of 300 rpm for 6 hours.

(57) Then, 40 mL of ethyl acetate is added to the obtained reactant to dissolve the raw material, the resultant, and the like, and filtration is performed using a membrane filter (manufactured by ADVANTEC, DISMIC (registered trademark), 13HP020AN, pore diameter 0.20 μm) to thereby obtain a reaction filtrate from which the catalyst Ru/C has been removed. In addition, the catalyst Ru/C used in the reaction is separately cleaned by 10 mL of ethyl acetate, and the cleaning liquid is recovered. The ratio of the raw material to the reactant is calculated by mixing the cleaning liquid with the previously obtained reaction filtrate and measuring by a gas chromatograph (manufactured by Shimadzu Corporation). Moreover, the post-reactants include DSTDK being the raw material, DSTDO being a monoreduced form, cis-DSTDD being a cis isomer of a direduced form, trans-DSTDD being a trans isomer of a direduced form, and others being by-products in which the cyclobutane skeleton is opened. The GC composition is shown in the table below.

Example 14

(58) (Example of Hydrogenation Under Pressurization by Ru/Al.sub.2O.sub.3)

(59) The same operations are carried out except that the catalyst of Example 13 is changed to 5 wt % Ru/Al.sub.2O.sub.3 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).

(60) The results of Examples 13 to 14 are shown in Table 4 below.

(61) TABLE-US-00004 TABLE 4 GC composition [GC %] DSTDD cis- trans- cis:trans Catalyst DSTDK DSTDO DSTDD DSTDD Others ratio Example 13 Ru/C containing 0.0 13.9 85.5 0.55 0.0 155.5:1 50 wt % of water Example 14 Ru/Al.sub.2O.sub.3 2.6 70.3 23.7 3.4 0.0  7.0:1

(62) The results of Examples 13 and 14 show that DSTDD can be quantitatively obtained from DSTDK by performing the catalytic hydrogenation reaction in a solid phase state without adding a solvent, and the cis ratio in DSTDD is as high as about 7 to about 155.

(63) According to the method for producing a cyclobutanediol compound according to the disclosure, a cyclobutanediol compound having a higher cis isomer ratio than before can be obtained under mild reaction conditions, and the producing process is environmentally friendly in terms of green chemistry because no reaction solvent is used.

INDUSTRIAL APPLICABILITY

(64) The cyclobutanediol compound having a high cis:trans ratio obtained by the method for producing a cyclobutanediol compound of the disclosure can be used as a raw material for polyester having high stability and stable quality in terms of glass transition temperature, impact strength, weather resistance, and hydrolysis stability.