JP7692312B2 - Cyclic carbonates, epoxides, and diols, and methods for their preparation - Google Patents

Description

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

Polycarbonate resin is an engineering plastic with excellent heat resistance, and there is a demand for it to have excellent heat resistance and optical properties as well as being lightweight and low cost. In order to meet such demands, there has been active development of special polycarbonate resins based on aromatic skeletons.

On the other hand, aliphatic, particularly polycarbonate resins having alicyclic structures, are being developed as alternatives to aromatic polycarbonates. Alicyclic polycarbonates tend to have better light resistance and optical properties than polycarbonate resins having aromatic rings such as bisphenol A. For example, Patent Document 1 discloses a polycyclic alicyclic polycarbonate resin that is excellent in transparency, heat resistance, and color tone. Polycarbonates using not only petroleum-derived raw materials but also raw materials derived from biomass such as plants are also being developed. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide, which can be derived from starch, as a raw material.

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 a benzene ring. It is widely known that poly(cyclohexene carbonate) can be synthesized by the reaction of cyclohexene oxide with carbon dioxide, as shown in Patent Document 3, for example. 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.

Patent No. 4774610 Patent No. 6507495 Patent No. 5403537 JP 2019-108547 A

Macromolecules 2014, 47, 4230-4235.

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 resins.

The present invention aims to provide novel cyclic carbonates, novel epoxides, and novel diols, as well as methods for producing them.

That is, the present invention is as follows.
[1]
The following formula (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, 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 form a cyclic structure together with the carbon element to which they are bonded, and in the cyclic structure, R ¹ to R ¹² are bonded to each other via an alkylene group or a carbonate group;
the alkylene group may be substituted with 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- or di-substituted methylene group;
n is an integer from 0 to 2.
A cyclic carbonate represented by the formula:
[2]
The cyclic carbonate according to [1], wherein R ¹ to 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.
[3]
The following formula (2):
(In formula (2), R ¹ to R ¹² are as defined in formula (1) above.)
The cyclic carbonate according to [1] or [2], represented by the formula:
[4]
The following formula (3):
The cyclic carbonate according to any one of [1] to [3], represented by the formula:
[5]
The cyclic carbonate according to [4], wherein the stereochemistry of the carbonate group is trans.
[6]
The following formula (4):
(In formula (4),
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, 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 form a cyclic structure together with the carbon element to which they are bonded, and in the cyclic structure, R ¹ to R ¹² are bonded to each other via an alkylene group or a carbonate group;
the alkylene group may be substituted with 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- or di-substituted methylene group;
n is an integer from 0 to 2.
An epoxide represented by the formula:
[7]
The epoxide according to [6], wherein R ¹ to 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.
[8]
The following formula (5):
(In formula (5), R ¹ to R ¹² are as defined in formula (4) above.)
The epoxide according to [6] or [7],
[9]
The following formula (6):
The epoxide according to any one of [6] to [8], represented by the formula:
[10]
The following formula (7):
(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 and 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; or R ¹ to R ¹² may form a cyclic structure together with the carbon element to which they are bonded, and in the cyclic structure, R ¹ to R ¹² are bonded to each other via an alkylene group or a carbonate group;
the alkylene group may be substituted with 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- or di-substituted methylene group;
n is an integer from 0 to 2.
A diol represented by the formula:
[11]
The diol according to [10], wherein R ¹ to 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.
[12]
The following formula (8):
(In formula (8), R ¹ to R ¹² are as defined in formula (7) above.)
The diol according to [10] or [11],
[13]
The following formula (9):
The diol according to any one of [10] to [12], represented by the formula:
[14]
The diol according to [13], wherein the two hydroxy groups are positioned trans relative to each other.
[15]
A method for producing the cyclic carbonate according to any one of [1] to [5], comprising a step of reacting the diol according to any one of [10] to [14] with a halogenated formate ester 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]
The method for producing an epoxide according to any one of [6] to [9], comprising:
(In formula (10), R ¹ to R ¹² , X, and n are as defined in formula (4) above.)
obtaining the epoxide by reacting with a peroxide.
[18]
A method for producing the diol according to any one of [10] to [14], comprising a step of obtaining the diol by hydrolyzing the epoxide according to any one of [6] to [9].
[19]
Use of the epoxide according to any one of [6] to [9] as a raw material for a polyether resin or a polycarbonate resin.
[20]
Use of the diol according to any one of [10] to [14] as a raw material for a polyester resin or a polycarbonate resin.

The present invention provides novel cyclic carbonates, novel epoxides, and novel diols, as well as methods for producing them.

1 shows the ¹ H-NMR spectrum of the epoxide in Example 1. 1 shows the ¹ H-NMR spectrum of the diol in Example 2. 1 shows the ¹³ C-NMR spectrum of the diol in Example 2. 1 shows the ¹ H-NMR spectrum of the cyclic carbonate in Example 3. 13 shows the ¹³ C-NMR spectrum of the cyclic carbonate in Example 3.

The following provides a detailed description of the embodiment of the present invention (hereinafter, also referred to as the "present embodiment"). Note that the present invention is not limited to the present embodiment, and can be modified in various ways within the scope of the gist of the present invention.

<Cyclic carbonate>
The cyclic carbonate of the present embodiment has a structure represented by the following formula (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 each independently represent 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 form a cyclic structure together with the carbon element to which they are bonded, 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 with 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. X is an unsubstituted, mono- or di-substituted methylene group, and n is an integer of 0 to 2 (preferably 1 or 2, more preferably 1). In this specification, the term "carbonate group" refers to a divalent substituent represented by -OC(=O)O-. When n is 0, the carbon atom to which R ⁴ is bonded and the carbon atom to which R ⁹ is bonded in formula (1) are not bonded.

The cyclic carbonate of this embodiment has excellent heat resistance due to the above configuration. The reasons for this are thought to be as follows, but are not limited to these.

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. In contrast, the cyclic carbonate of the present embodiment has a polycyclic structure in which multiple alicyclic structures are condensed, and the skeleton is rigid, so it is presumed that it has excellent heat resistance.

In this embodiment, in formula (1), R ¹ to 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. From the viewpoint of more effectively and reliably achieving the effects of the present invention, in formula (1), R ¹ to R ¹² are preferably each independently 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 to R ¹² are more preferably each independently 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 to R ¹² are even more preferably each independently 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.

In this embodiment, in formula (1), R ¹ to 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 with a hydroxyl group, a phosphate group, an alkoxy group, or an ester group. From the viewpoint of more reliably and effectively achieving the effects of the present invention, when R ¹ to R ¹² are bonded to each other via an alkylene group to form a cyclic structure, the number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 12. Furthermore, 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, when R ¹ to R ¹² form a cyclic structure, the cyclic structure is preferably formed via an unsubstituted alkylene group. Examples of unsubstituted alkylene groups include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,3-cyclopentylene, 1,6-hexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene groups.

When R ¹ to R ¹² form a cyclic structure, it is preferable that any two of R ¹ to R ¹² are combined to form a cyclic structure.

The phosphate group in the above formula (1) of this 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 reliably achieving the effects of the present invention, when the phosphate group is substituted, it is preferable that the substituent is an unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. From the same viewpoint, it is preferable that the phosphate group in this embodiment is unsubstituted.

The aryl group having 6 to 20 carbon atoms in the above formula (1) of this embodiment is not particularly limited, but examples thereof include unsubstituted or alkyl-containing aryl groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, propylphenyl, and diisopropylphenyl groups, aryl groups having alkoxy groups such as 4-methoxyphenyl and 3,5-dimethoxyphenyl groups, and biphenyl, naphthyl, and anthracenyl groups.

The aralkyl group having 6 to 20 carbon atoms in the above formula (1) of this embodiment is not particularly limited, but examples thereof include unsubstituted or alkyl group-containing aralkyl groups such as benzyl group, 4-methylbenzyl group, and phenethyl group, alkoxy group-containing aralkyl groups such as 4-methoxybenzyl group and 3,5-dimethoxybenzyl group, and diphenylmethyl group, naphthylmethyl group, and anthracenylmethyl group.

In the above formula (1) of this embodiment, the alkoxy group having 1 to 10 carbon atoms is not particularly limited, but examples thereof include 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.

In the above formula (1) of this embodiment, the silyl group having 1 to 30 carbon atoms is not particularly limited, but examples thereof include 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.

In the above formula (1) of this embodiment, the silylalkoxy group having 1 to 30 carbon atoms is not particularly limited, but examples thereof include a trimethylsilylmethoxy group, a trimethylsilylethoxy group, a trimethylsilylphenoxy group, a trimethylsilylbenzyloxy group, a triethylsilylmethoxy group, a triethylsilylethoxy group, a triethylsilylphenoxy group, a triethylsilylbenzyloxy group, a triisopropylsilylmethoxy group, a triisopropylsilylethoxy group, a triisopropylsilylphenoxy group, a triisopropylsilylbenzyloxy group, a triphenylsilylmethoxy group, a triphenylsilylethoxy group, a triphenylsilylphenoxy group, a triphenylsilyl These include a tert-butyldimethylsilyl methoxy group, a tert-butyldimethylsilyl ethoxy group, a tert-butyldimethylsilyl phenoxy group, a tert-butyldimethylsilyl benzyloxy group, a di-tert-butylisobutylsilyl methoxy group, a di-tert-butylisobutylsilyl ethoxy group, a di-tert-butylisobutylsilyl phenoxy group, a di-tert-butylisobutylsilyl benzyloxy group, a tert-butyldiphenylsilyl methoxy group, a tert-butyldiphenylsilyl ethoxy group, a tert-butyldiphenylsilyl phenoxy group, and a tert-butyldiphenylsilyl benzyloxy group.

In the above formula (1) of this embodiment, the ester group having 1 to 11 carbon atoms is not particularly limited, but examples thereof include a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group, a cyclopentyl ester group, a hexyl ester group, a cyclohexyl ester group, a heptyl ester group, an octyl ester group, a nonanyl ester group, a decyl ester group, a phenyl ester group, a benzyl ester group, a vinyl ester group, and an allyl ester group.

In the above formula (1) of this embodiment, the acyl group having 1 to 11 carbon atoms is not particularly limited, but examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a benzoyl group.

In the above formula (1) of this 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-nonanyl group, an n-decyl group, a 1-adamantyl group, and a 2-adamantyl group.

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

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

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 explained in relation to formula (1). The stereochemistry around the asymmetric carbon marked with * 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.

From the viewpoint of improving 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).
(In formula (2), R ¹ to R ¹² are as explained in relation to formula (1) above.)

<Epoxide>
The epoxide of the present embodiment has a structure represented by the following formula (4).

In formula (4), ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12 , X, and n are as explained in relation to formula (1).

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

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 explained in relation to formula (1). The stereochemistry around the asymmetric carbon marked with * may be either R or S.

From the viewpoint of improving 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).
(In formula (5), R ¹ to R ¹² are as explained in relation to formula (1) above.)

<Diol>
The diol of the present embodiment has a structure represented by the following formula (7).

In formula (7), ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12 , X, and n are as described in relation to formula (1).

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).

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 explained in relation to formula (1). The stereochemistry around the asymmetric carbon marked with * may be either R or S. Although not particularly limited, diols represented by (F1) to (F2) and (F5) to (F6) in which two hydroxy groups are located in trans-position relative to each other are preferred.

From the viewpoint of improving 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).
(In formula (8), R ¹ to R ¹² are as explained in relation to formula (1) above.)

<Production method 1 of cyclic carbonate>
The method for producing a cyclic carbonate of this embodiment includes a step of reacting a diol represented by any one of the formulas (7) to (9) with a halogenated formate ester or a carbonate ester to obtain the cyclic carbonate.

(Halogenated formates)
In the present embodiment, the halogenated formate ester is not particularly limited, but examples thereof include methyl chloroformate, ethyl chloroformate, methyl bromoformate, ethyl bromoformate, methyl iodoformate, and ethyl iodoformate.

(carbonate ester)
In the present embodiment, the carbonate ester is not particularly limited, but 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.

(Carbonation catalyst)
In the present embodiment, a base catalyst may be used in the step of reacting the diol represented by any one of the formulae (7) to (9) with a halogenated formate ester or a carbonate ester. The base catalyst is not particularly limited, but examples thereof include organic bases such as cyclic amines 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 organic base is not particularly limited, but 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]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), diphenylguanidine (DPG), N,N-dimethyl-4-aminopyridine (DMAP), imidazole, pyrimidine, and purine.

(solvent)
In the method for producing a cyclic carbonate of the present embodiment, a solvent may be used. The solvent is not particularly limited, but examples thereof include ether-based 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-based solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane, saturated hydrocarbon-based solvents such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane, aromatic hydrocarbon-based solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol, and ketone-based solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone, and methyl isobutyl ketone.

<Production method 2 of cyclic carbonate>
The cyclic carbonate of the present embodiment can also be obtained by reacting an epoxide represented by any one of the above formulas (4) to (6) with carbon dioxide.

<Epoxide Production Method>
The method for producing an epoxide according to the present embodiment includes a step of reacting a cyclic olefin represented by the following formula (10) with a peroxide to obtain the epoxide.

In formula (10), ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12 , X, and n are as explained in relation to formula (1).

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

<Method of producing diol>
The method for producing a diol according to the present embodiment includes a step of obtaining the diol by hydrolyzing an epoxide represented by any one of the formulas (4) to (6).

The present invention will be explained in more detail using examples, but the present invention is not limited to these examples.

In this specification, the analysis of cyclic carbonates, epoxides, and diols was performed as follows.

(NMR measurement)
NMR measurements were performed as follows using a JEOL NMR device (product name: ECZ400S) and a TFH probe to obtain ¹ H-NMR and ¹³ C-NMR spectra of cyclic carbonates, epoxides, and diols. The reference peaks of the deuterated solvents were δ _H 7.26 ppm and δ _C 77.0 ppm when chloroform-d was used, and δ _C 39.5 ppm when dimethylsulfoxide-d ₆ was used. The measurements were performed with 32 integrations for ¹ H-NMR and 4,000 integrations for ¹³ C-NMR.

[Example 1]
Synthesis of 4,5-epoxy-tricyclo[6.2.1.0 ^2.7 ]undecane
Under an argon atmosphere, 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) were added to a 2 L four-neck flask, and the mixture was stirred with a mechanical stirrer using a stirring blade. The reaction solution was cooled by immersing it in an ice bath. m-Chloroperbenzoic acid (45.6 g, 185.2 mmol) was added in three portions. After the addition was completed, the mixture was gradually warmed to room temperature while still immersed in ice water. After stirring for 19 hours, the reaction solution was filtered under reduced pressure, and the residue was rinsed with chloroform (500 mL x 3). The filtrate was washed with saturated aqueous sodium thiosulfate solution (500 mL), saturated aqueous sodium hydrogen carbonate solution (500 mL), and saturated saline solution (500 mL), and dried over sodium sulfate. The dried organic layer was concentrated using an evaporator. The resulting 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 H-NMR spectrum of the compound was as follows. The NMR chart is shown in Figure 1.
¹ H-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).

[Example 2]
Synthesis of 4,5-dihydroxy-tricyclo[6.2.1.0 ^2.7 ]undecane
In a 500 mL four-neck flask, 4,5-epoxy-tricyclo[6.2.1.0 ^2.7 ]undecane (25.2 g, 6.09 mmol), ion-exchanged water (250 mL), and a stir bar were placed, 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 product as a white solid (25.0 g). ^{The 1} H-NMR spectrum and ¹³ C-NMR spectrum of the compound were as follows. The NMR charts are shown in Figures 2 and 3.
¹ H-NMR (CDCl 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 C-NMR ((CD ₃ ) ₂ SO): δ _C 29.2, 32.4, 32.5, 33.4, 36.0, 40.5, 41.3, 41.4, 73.6, 74.3.

[Example 3]
Synthesis of 4,5-carbonato-tricyclo[6.2.1.0 ^2.7 ]undecane
Under argon flow, 4,5-dihydroxy-tricyclo[6.2.1.0 ^2.7 ]undecane (20.0 g, 110.0 mmol) and dehydrated tetrahydrofuran (200 mL) were added to a 500 mL four-neck flask, and the mixture was stirred with a mechanical stirrer using a stirring blade. The reaction solution was cooled by immersing it in a salt ice bath. Ethyl chloroformate (23.8 g, 219.1 mmol) was slowly added. Triethylamine (29.9 g, 295.8 mmol) was diluted in dehydrated toluene (65 mL) and slowly dropped using a dropping funnel. After stirring at room temperature for 18 hours, 40 g of silica gel was filled into a Kiriyama funnel, and the reaction solution was slowly poured into it. After passing the liquid through the funnel, the filter cake was rinsed with tetrahydrofuran/toluene (2/1) (200 mL x 5), and the filtrate was concentrated using an evaporator. The obtained concentrate was dissolved in chloroform (250 mL), ion-exchanged water (250 mL) was added, and the mixture was stirred, and then the organic layer was collected. The collected 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 dropped into ice-cooled heptane (460 mL). After stirring for 30 minutes, the precipitated solid was collected by vacuum filtration, and then dried under reduced pressure at 40° C. for 48 hours to obtain the target product as a white solid (15.1 g). The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the compound were as follows. The NMR charts are shown in FIG. 4 and FIG. 5.
¹ H-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 C-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.

The cyclic carbonates, epoxides, and diols 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 the field of various resin materials, etc.

Claims (6)

The following formula (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- or di-substituted methylene group;
n is 1 or 2 .
A cyclic carbonate represented by the formula: The following formula (2):

(In formula (2), R ¹ to R ¹² are as defined in formula (1) above.)
The cyclic carbonate according to claim 1 , wherein The following formula (3):

The cyclic carbonate according to claim 1 or 2 , wherein The cyclic carbonate of claim 3 , wherein the stereochemistry of the carbonate group is trans. A method for producing the cyclic carbonate according to any one of claims 1 to 4 , comprising the step of reacting a diol represented by the following formula (7) with a halogenated formate ester or a carbonate ester to obtain the cyclic carbonate:

(In formula (7), R ¹ to R ¹² , X, and n are as defined in formula (1) above.)
Manufacturing method. A method for producing the cyclic carbonate according to any one of claims 1 to 4 , comprising the step of reacting an epoxide represented by the following formula (4) with carbon dioxide to obtain the cyclic carbonate:

(In formula (4), R ¹ to R ¹² , X, and n are as defined in formula (1) above.)
Manufacturing method.