Cyclic carbonates, epoxides, and diols, and methods for producing them

Abstract

To provide a cyclic carbonate that serves as raw material for polycarbonate resin, an epoxide, and a diol and methods for producing them.SOLUTION: A cyclic carbonate is represented by the following formula (1) (where, in the formula (1), R1-R12 independently represent a hydrogen atom, a hydroxy group, a phosphate group, a C6-20 aryl group, a C6-20 aralkyl group, a C1-10 alkoxy group, a C1-30 silyl group, a C1-30 silyl alkoxy group, a C1-11 ester group, a C1-11 acyl group or the like, X is an unsubstituted, monosubstituted or disubstituted methylene group, and n is an integer of 0-2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to cyclic carbonates, epoxides, and diols, and methods for producing them.

Background Art

[0002] Polycarbonate resins are engineering plastics with excellent heat resistance, and there is a demand for those that combine excellent heat resistance and optical properties while being lightweight and low-cost. For the purpose of meeting such demands, the development of special polycarbonate resins based on aromatic skeletons has been actively carried out.

[0003] On the other hand, as a resin alternative to aromatic polycarbonates, the development of polycarbonate resins having an aliphatic, particularly alicyclic structure, has also been carried out. Alicyclic polycarbonates tend to be superior in light resistance and optical properties compared to polycarbonate resins having an aromatic ring such as bisphenol A. For example, Patent Document 1 discloses a polycyclic alicyclic polycarbonate resin excellent in transparency, heat resistance, and color tone. In addition, the development of polycarbonates using not only petroleum raw materials but also raw materials derived from biomass such as plants has been carried out. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide derivable from starch as a raw material.

[0004] Among such alicyclic polycarbonate resins, poly(cyclohexene carbonate) having a cyclohexane carbonate structure is the simplest polycarbonate having a saturated six-membered carbon ring corresponding to the benzene ring. It is widely known that poly(cyclohexene carbonate) can be synthesized by the reaction of cyclohexene oxide and carbon dioxide, as shown in, for example, Patent Document 3. It is also known that poly(cyclohexene carbonate) can be obtained by ring-opening polymerization of 1,2-cyclohexene carbonate, as described in Patent Document 4 and Non-Patent Document 1.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Japanese Patent No. 4774610 [Patent Document 2] Japanese Patent No. 6507495 [Patent Document 3] Japanese Patent No. 5403537 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2019 - 108547 [Non - Patent Document]

[0006] [Non - Patent Document 1] Macromolecules 2014, 47, 4230 - 4235. [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] Polycarbonate resins are required to have various physical properties, and new substances are required for the cyclic carbonates, epoxides, and diols used as raw materials for the resin.

[0008] An object of the present invention is to provide a novel cyclic carbonate, a novel epoxide, a novel diol, and methods for producing them.

[0009] That is, the present invention is as follows. [1] The following formula (1): [Chemical formula] (In formula (1), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 and R12 is each independently a hydrogen atom, a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R 1 ~R 12 may, together with the carbon element to which they are attached, form a cyclic structure, and in the cyclic structure, R 1 ~R 12 are bonded to each other via an alkylene group or a carbonate group, the alkylene group may be substituted by a hydroxyl group, a phosphate group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, X is an unsubstituted, mono-substituted or di-substituted methylene group, n is an integer from 0 to 2.) A cyclic carbonate represented by [2] R 1 ~R 12 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, the cyclic carbonate according to [1]. [3] The following formula (2):

Chemical formula

Chemical formula

Chemical formula

[10] The following formula (7):

Chemical formula

[11] R 1 ~R 12 are, independently of each other, a hydrogen atom, a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, the diol according to

[10] .

[12] The following formula (8):

Chemical formula

[10] or

[11] .

[13] The following formula (9): [Chemical formula] The diol according to any one of

[10] to

[12] , represented by

[14] The diol according to

[13] , in which two hydroxy groups are trans to each other.

[15] A method for producing a cyclic carbonate according to any one of [1] to [5], comprising a step of reacting a diol according to any one of

[10] to

[14] with a formate halide or a carbonate ester to obtain the cyclic carbonate.

[16] A method for producing a cyclic carbonate according to any one of [1] to [5], comprising a step of reacting an epoxide according to any one of [6] to [9] with carbon dioxide to obtain the cyclic carbonate.

[17] A method for producing an epoxide according to any one of [6] to [9], comprising a step of reacting a cyclic olefin represented by the following formula (10) with [Chemical formula] (In formula (10), R 1 ~R 12 , X, and n are as defined in the above formula (4).) a peroxide to obtain the epoxide.

[18] A method for producing a diol according to any one of

[10] to

[14] , comprising a step of hydrolyzing an epoxide according to any one of [6] to [9] to obtain the diol.

[19] Use of an epoxide according to any one of [6] to [9] as a raw material for a polyether resin or a polycarbonate resin.

[20] Use of a diol according to any one of

[10] to

[14] as a raw material for a polyester resin or a polycarbonate resin.

Advantages of the Invention

[0010] According to the present invention, novel cyclic carbonates, novel epoxides, and novel diols, and methods for producing them are provided.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0012] Hereinafter, modes for carrying out the present invention (hereinafter, also referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the present embodiment, and various modifications can be made and implemented within the scope of the gist thereof.

[0013] <Cyclic Carbonate> The cyclic carbonate of the present embodiment has a structure represented by the following formula (1).

Chemical formula

[0014] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10, R 11 , R 12 is, independently of each other, a hydrogen atom, a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R 1 to R 12 may, together with the carbon element to which they are attached, form a cyclic structure, and in the cyclic structure, R 1 to R 12 are bonded to each other via an alkylene group or a carbonate group, and the alkylene group may be substituted by a hydroxyl group, a phosphate group, an amino group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Further, X is an unsubstituted, mono-substituted or di-substituted methylene group, and n is an integer of 0 to 2 (preferably 1 or 2, more preferably 1). In the present specification, the "carbonate group" means a divalent substituent represented by -OC(=O)O-. When n is 0, the carbon atom to which R 4 is attached and the carbon atom to which R 9 is attached are not bonded to each other.

[0015] The cyclic carbonate of the present embodiment has excellent heat resistance by having the above configuration. The reason is considered as follows, but the reason is not limited thereto.

[0016] Conventional cyclic carbonates having an alicyclic structure have a cyclic skeleton, but the structural freedom of the cycloalkane skeleton is relatively high, and due to this structure, the heat resistance is low. On the other hand, the cyclic carbonate of the present embodiment has a polycyclic structure in which a plurality of alicyclic structures are fused, and it is presumed that the skeleton becomes rigid, so that it has excellent heat resistance.

[0017] In the present embodiment, in formula (1), R 1 to R12 is, independently of each other, a hydrogen atom, a hydroxyl group, a phosphate group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of more effectively and surely achieving the effects of the present invention, in formula (1), R 1 ~R 12 is preferably, independently of each other, one or more substituents selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. From the same viewpoint, in formula (1), R 1 ~R 12 is more preferably, independently of each other, one or more substituents selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. From the same viewpoint, in formula (1), R 1 ~R 12 is still more preferably, independently of each other, one or more substituents selected from the group consisting of a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, and an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

[0018] In the present embodiment, in formula (1), R 1 ~R 12 may be bonded to each other via an alkylene group or a carbonate group (-OC(=O)O- group) to form a cyclic structure, and the alkylene group may be substituted by a hydroxyl group, a phosphate group, an alkoxy group, or an ester group. From the viewpoint of more surely and effectively achieving the effects of the present invention, R 1 ~R 12When they are bonded to each other via an alkylene group to form a cyclic structure, the number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12. Further, from the same viewpoint, the substituent of the alkylene group is preferably a hydroxyl group, an alkoxy group, or an ester group, and more preferably a hydroxyl group or an alkoxy group. From the same viewpoint, R 1 ~R 12 When forming a cyclic structure, preferably, a cyclic structure is formed via an unsubstituted alkylene group. Examples of the unsubstituted alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,3-cyclopentylene group, a 1,6-hexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.

[0019] R 1 ~R 12 When forming a cyclic structure, it is preferable that any two of R 1 ~R 12 are combined together to form a cyclic structure.

[0020] The phosphate group in the above formula (1) of the present embodiment may be unsubstituted or substituted. That is, it may be a monosubstituted phosphate group or a disubstituted phosphate group. From the viewpoint of more effectively and surely achieving the effects of the present invention, when the phosphate group is substituted, the substituent is preferably an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. From the same viewpoint, the phosphate group in the present embodiment is preferably unsubstituted.

[0021] In the above formula (1) of the present embodiment, the aryl group having 6 to 20 carbon atoms is not particularly limited. For example, it includes aryl groups having no substituent or an alkyl group, such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a propylphenyl group, a diisopropylphenyl group, etc.; aryl groups having an alkoxy group, such as a 4-methoxyphenyl group, a 3,5-dimethoxyphenyl group, etc.; and aryl groups such as a biphenyl group, a naphthyl group, and an anthracenyl group.

[0022] In the above formula (1) of the present embodiment, the aralkyl group having 6 to 20 carbon atoms is not particularly limited. For example, it includes aralkyl groups having no substituent or an alkyl group, such as a benzyl group, a 4-methylbenzyl group, a phenethyl group, etc.; aralkyl groups having an alkoxy group, such as a 4-methoxybenzyl group, a 3,5-dimethoxybenzyl group, etc.; and aralkyl groups such as a diphenylmethyl group, a naphthylmethyl group, and an anthracenylmethyl group.

[0023] In the above formula (1) of the present embodiment, the alkoxy group having 1 to 10 carbon atoms is not particularly limited. For example, it includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a nonanyloxy group, a decyloxy group, a phenoxy group, a benzyloxy group, a vinyloxy group, and an allyloxy group.

[0024] In the above formula (1) of the present embodiment, the silyl group having 1 to 30 carbon atoms is not particularly limited. For example, it includes a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, a di-tert-butylisobutylsilyl group, and a tert-butyldiphenylsilyl group.

[0025] In the above formula (1) of the present embodiment, the silylalkoxy group having 1 to 30 carbon atoms is not particularly limited. For example, trimethylsilylmethoxy group, trimethylsilylethoxy group, trimethylsilylphenoxy group, trimethylsilylbenzyloxy group, triethylsilylmethoxy group, triethylsilylethoxy group, triethylsilylphenoxy group, triethylsilylbenzyloxy group, triisopropylsilylmethoxy group, triisopropylsilylethoxy group, triisopropylsilylphenoxy group, triisopropylsilylbenzyloxy group, triphenylsilylmethoxy group, triphenylsilylethoxy group, triphenylsilylphenoxy group, triphenylsilylbenzyloxy group, tert-butyldimethylsilylmethoxy group, tert-butyldimethylsilylethoxy group, tert-butyldimethylsilylphenoxy group, tert-butyldimethylsilylbenzyloxy group, di-tert-butylisobutylsilylmethoxy group, di-tert-butylisobutylsilylethoxy group, di-tert-butylisobutylsilylphenoxy group, di-tert-butylisobutylsilylbenzyloxy group, tert-butyldiphenylsilylmethoxy group, tert-butyldiphenylsilylethoxy group, tert-butyldiphenylsilylphenoxy group, and tert-butyldiphenylsilylbenzyloxy group can be mentioned.

[0026] In the above formula (1) of the present embodiment, the ester group having 1 to 11 carbon atoms is not particularly limited. For example, methyl ester group, ethyl ester group, propyl ester group, butyl ester group, pentyl ester group, cyclopentyl ester group, hexyl ester group, cyclohexyl ester group, heptyl ester group, octyl ester group, nonanyl ester group, decyl ester group, phenyl ester group, benzyl ester group, vinyl ester group, and allyl ester group can be mentioned.

[0027] In the above formula (1) of the present embodiment, the acyl group having 1 to 11 carbon atoms is not particularly limited. For example, formyl group, acetyl group, propionyl group, butyryl group, valeryl group, and benzoyl group can be mentioned.

[0028] In the above formula (1) of the present embodiment, examples of the unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a 1-norbornyl group, a 2-norbornyl group, an n-octyl group, a 1-bicyclo[2.2.2]octyl group, a 2-bicyclo[2.2.2]octyl group, an n-nonanil group, an n-decyl group, a 1-adamantyl group, and a 2-adamantyl group.

[0029] In the above formula (1) of the present embodiment, the unsubstituted, mono-substituted, or di-substituted methylene group represented by X is not particularly limited, and examples thereof include a methylene group, a methylmethylene group, and a dimethylmethylene group.

[0030] In the cyclic carbonate of the present embodiment, the cyclic carbonate represented by the formula (1) includes cyclic carbonates (B1) to (B8) represented by the following formulas (1-1) to (1-8).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0031] In Formulas (1-1) to (1-8), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , X, and n are as described in relation to Formula (1). Note that the stereochemistry around the asymmetric carbon indicated by * may be either R or S. Although not particularly limited, cyclic carbonates represented by (B1) to (B2) and (B5) to (B6) in which the stereochemistry of the carbonate group is trans are preferred.

[0032] From the viewpoint of enhancing heat resistance, the compound represented by the above Formula (1) is preferably a compound represented by the following Formula (2), and more preferably a compound represented by the following Formula (3).

Chemical formula

Chemical formula

[0033] <Epoxide> The epoxide of this embodiment has a structure represented by the following Formula (4).

Chemical formula

[0034] In Formula (4), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R9 , R 10 , R 11 , R 12 , X, and n are as described in relation to formula (1).

[0035] In the epoxide of this embodiment, the epoxide represented by formula (4) includes epoxides (D1) to (D4) represented by the following formulas (4-1) to (4-4).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0036] In formulas (4-1) to (4-4), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , X, and n are as described in relation to formula (1). Note that the stereochemistry around the asymmetric carbon indicated by * may be either R or S.

[0037] From the viewpoint of enhancing heat resistance, the compound represented by the above formula (4) is preferably a compound represented by the following formula (5), and more preferably a compound represented by the following formula (6).

Chemical formula

Chemical formula

[0038] <Diol> The diol of this embodiment has a structure represented by the following formula (7). [Chemical formula]

[0039] In formula (7), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , X, and n are as described in the relationship with formula (1).

[0040] In the diol of this embodiment, the diol represented by formula (7) includes epoxides (F1) to (F8) represented by the following formulas (7-1) to (7-8). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0041] In formulas (7-1) to (7-8), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , X, and n are as described in the relationship with formula (1). The stereochemistry around the asymmetric carbon indicated by * may be either R or S. Although not particularly limited, the diols represented by (F1) to (F2) and (F5) to (F6) in which two hydroxy groups are located trans to each other are preferred.

[0042] From the viewpoint of enhancing heat resistance, the compound represented by the above formula (7) is preferably a compound represented by the following formula (8), and more preferably a compound represented by the following formula (9). [Chemical formula] (In formula (8), R 1 ~R 12 are as described in the relationship with the above formula (1).) [Chemical formula]

[0043] [Production method 1 of cyclic carbonate] The production method of the cyclic carbonate of the present embodiment has a step of obtaining the cyclic carbonate by reacting the diol represented by the above formulas (7) to (9) with a formate halide or a carbonate ester.

[0044] (Formate halide) In this embodiment, the formate halide is not particularly limited, and examples thereof include methyl chloroformate, ethyl chloroformate, methyl bromoformate, ethyl bromoformate, methyl iodoformate, and ethyl iodoformate.

[0045] (Carbonate ester) In this embodiment, the carbonate ester is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, propyl carbonate, isopropyl carbonate, butyl carbonate, isobutyl carbonate, pentyl carbonate, isopentyl carbonate, cyclopentyl carbonate, hexyl carbonate, isohexyl carbonate, cyclohexyl carbonate, diphenyl carbonate, p-nitrophenyl carbonate, and dibenzyl carbonate.

[0046] (Carbonation catalyst) In this embodiment, in the step of reacting the diol represented by the above formulas (7) to (9) with a formate halide or a carbonate ester, a base catalyst may be used. The base catalyst is not particularly limited, and examples thereof include organic bases such as cyclic monoamines and cyclic diamines (particularly cyclic diamine compounds having an amidine skeleton), triamine compounds having a guanidine skeleton, and heterocyclic compounds containing a nitrogen atom. The above organic bases are not particularly limited, and examples thereof include triethylamine, diisopropylethylamine, 1,4-diazabicyclo-[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD), diphenylguanidine (DPG), N,N-dimethyl-4-aminopyridine (DMAP), imidazole, pyrimidine, and purine.

[0047] (Solvent) In the method for producing a cyclic carbonate according to this embodiment, a solvent may be used. The solvent is not particularly limited, and examples thereof include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, tert-butyl methyl ether, diisopropyl ether, cyclopentyl methyl ether, and propylene glycol monomethyl ether acetate; halogen solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane; saturated hydrocarbon solvents such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol; and ketone solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone, and methyl isobutyl ketone.

[0048] <Method for Producing Cyclic Carbonate 2> The cyclic carbonate according to this embodiment can also be obtained by reacting an epoxide represented by the above formulas (4) to (6) with carbon dioxide.

[0049] <Method for Producing Epoxide> The method for producing an epoxide according to this embodiment includes a step of obtaining the epoxide by reacting a cyclic olefin represented by the following formula (10) with a peroxide.

[0050] [Chemical formula]

[0051] In formula (10), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 , R 11 , R 12 , X, and n are as described in relation to formula (1).

[0052] (Peroxide) In this embodiment, the peroxide is not particularly limited, and examples thereof include hydrogen peroxide, tert-butyl hydroperoxide, m-chloroperbenzoic acid, and dimethyldioxirane.

[0053] (Method for producing diol) The method for producing a diol according to this embodiment includes a step of obtaining the diol by hydrolyzing the epoxide represented by the above formulas (4) to (6).

Example

[0054] The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples etc. at all.

[0055] In this specification, the analysis of cyclic carbonate, epoxide, and diol was performed as follows.

[0056] (NMR measurement) Using an NMR apparatus (product name: ECZ400S) manufactured by JEOL Ltd. and a TFH probe, NMR measurement was performed as follows to obtain the 1 1H-NMR spectrum 13 and the 13C-NMR spectrum of cyclic carbonate, epoxide, and diol. The reference peak of the deuterated solvent was δ H 7.26 ppm when chloroform-d was used, and δ C 77.0 ppm, and when dimethyl sulfoxide-d 6 was used, it was assumed to be δ C 39.5 ppm. The number of integrations was 1 32 times for 1H-NMR 13 and 4000 times for 13C-NMR for the measurement.

[0057] [Example 1] (Synthesis of (4,5-epoxy-tricyclo[6.2.1.0 2.7 undecane)) Under an argon stream, to a 2 L four-necked flask were added tricyclo[6.2.1.0 2.7 undec-4-ene (24.1 g, 162.4 mmol), sodium hydrogen carbonate (14.7 g, 175.4 mmol), and chloroform (770 mL). Using a stirring blade, the mixture was stirred with a mechanical stirrer. The reaction solution was immersed in an ice bath for cooling. m-Chloroperbenzoic acid (45.6 g, 185.2 mmol) was added in three portions. After the addition was complete, while immersed in ice water, the temperature was gradually raised to room temperature. After stirring for 19 hours, the reaction solution was filtered under reduced pressure, and the residue was rinsed with chloroform (500 mL × 3). The filtrate was washed with a saturated aqueous solution of sodium thiosulfate (500 mL), a saturated aqueous solution of sodium hydrogen carbonate (500 mL), and saturated brine (500 mL), and dried over sodium sulfate. The dried organic layer was concentrated using an evaporator. The obtained concentrate was subjected to column chromatography using 318 g of amino silica gel to obtain the target product as a colorless transparent liquid (25.6 g). The 1 1H-NMR spectrum of the compound was as follows. The NMR chart is shown in Figure 1. 1 1H-NMR(CDCl 3 ): δ H 1.00 - 1.05 (1H), 1.13 - 1.23 (2H), 1.33 - 1.69 (7H), 1.81 - 1.84 (2H), 2.10 - 2.20 (2H), 3.05 - 3.08 (2H).

[0058] [Example 2] (Synthesis of (4,5-dihydroxy-tricyclo[6.2.1.0 2.7 undecane)) To a 500 mL four-necked flask was added (4,5-epoxy-tricyclo[6.2.1.0 2.7Undecane (25.2 g, 6.09 mmol), ion-exchanged water (250 mL), and a stir bar were added, and the mixture was stirred with a magnetic stirrer. The reaction solution was immersed in an oil bath and heated to an external temperature of 100 °C. After stirring for 18 hours, the reaction solution was concentrated under reduced pressure using an evaporator and azeotroped three times with acetonitrile to obtain the target white solid (25.0 g). The 1 1H-NMR spectrum, 13 13C-NMR spectrum was as follows. The NMR charts are shown in Figures 2 and 3. 1 1H-NMR (CDCl 3 3): δ H 1.00 - 1.09 (2H), 1.16 - 1.25 (2H), 1.46 - 1.75 (8H), 1.85 (1H), 1.93 (1H), 2.07 (1H), 2.15 (1H), 3.48 - 3.54 (1H), 3.78 - 3.82 (1H). 13 13C-NMR ((CD 3 3)2 2 SO): δ C 29.2, 32.4, 32.5, 33.4, 36.0, 40.5, 41.3, 41.4, 73.6, 74.3.

[0059] [Example 3] (Synthesis of (4,5-carbonato-tricyclo[6.2.1.0 2.7 undecane)) Under an argon stream, 4,5-dihydroxy-tricyclo[6.2.1.0 2.7Undecane (20.0 g, 110.0 mmol) and dehydrated tetrahydrofuran (200 mL) were added, and the mixture was stirred with a mechanical stirrer using a stirring blade. The reaction solution was immersed in a salt-ice bath and cooled. Ethyl chloroformate (23.8 g, 219.1 mmol) was slowly added. Triethylamine (29.9 g, 295.8 mmol) was diluted with dehydrated toluene (65 mL) and slowly added dropwise with a dropping funnel. After stirring at room temperature for 18 hours, a Celite funnel was filled with 40 g of silica gel, and the reaction solution was slowly poured in. After passing the solution, the filtrate was rinsed with tetrahydrofuran / toluene (2 / 1) (200 mL × 5), and the filtrate was concentrated with an evaporator. The obtained concentrate was dissolved in chloroform (250 mL), ion-exchanged water (250 mL) was added and stirred, and then the organic layer was recovered. The recovered organic layer was washed with ion-exchanged water (250 mL), and the washed organic layer was dried over magnesium sulfate and filtered. The filtrate was concentrated with an evaporator. The obtained concentrate was dissolved again in chloroform (46 mL) and slowly added dropwise into ice-cooled heptane (460 mL). After stirring for 30 minutes, the precipitated solid was recovered by vacuum filtration and dried under reduced pressure at 40 °C for 48 hours to obtain the target white solid (15.1 g). The 1 1H-NMR spectrum, 13 13C-NMR spectrum was as follows. The NMR charts are shown in Figures 4 and 5. 1 1H-NMR (CDCl 3 ): δ H 1.13 - 1.26 (3H), 1.31 - 1.39 (2H), 1.44 - 1.61 (2H), 1.88 - 2.10 (5H), 2.22 - 2.26 (1H), 2.47 - 2.54 (1H), 3.91 - 4.09 (2H). 13 13C-NMR (CDCl 3 ): δ C 27.1, 31.2, 33.0, 33.1, 36.0, 39.9, 42.4, 43.0, 45.8, 81.4, 81.5, 155.1.

Industrial Applicability

[0060] The cyclic carbonate, epoxide, and diol of the present invention can be used as raw materials for polycarbonate resins, polyether resins, polyester resins, polyurethane resins, etc., and have industrial applicability in fields such as various resin materials.

Claims

1. The following formula (1): 【Chemical 1】 (In formula (1), R １ 、 R ２ 、 R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ 、 R ９ 、 R １０ 、 R １１ 、 and R １２ are each independently a hydrogen atom, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, X is an unsubstituted, mono-substituted or di-substituted methylene group, n is 1 or 2.) A cyclic carbonate represented by the formula.

2. The following formula (2): 【Chemical 2】 (In formula (2), R １ to R １２ are as defined in the above formula (1).) The cyclic carbonate according to Claim 1, represented by the formula.

3. The following formula (3): 【Chemical Formula 3】 The cyclic carbonate according to Claim 1 or 2, represented by the formula.

4. The cyclic carbonate according to Claim 3, wherein the stereochemistry of the carbonate group is trans.

5. A method for producing the cyclic carbonate according to any one of Claims 1 to 4, comprising a step of reacting a diol represented by the following formula (7) with a halogen formate ester or a carbonate ester to obtain the cyclic carbonate, 【Chemical Formula 4】 (In formula (7), R1 to R12, X, and n are as defined in the above formula (1).) Production method.

6. A method for producing the cyclic carbonate according to any one of Claims 1 to 4, comprising a step of reacting an epoxide represented by the following formula (4) with carbon dioxide to obtain the cyclic carbonate, 【Chemical Formula 5】 (In formula (4), R1 to R12, X, and n are as defined in the above formula (1).) Production method.

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