RU2771748C2 - Method for producing carbonate derivative - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing a carbonate derivative, including irradiation with light of a composition, containing halogenated methane having one or more types of halogen atoms selected from a group consisting of a chlorine atom, a bromine atom and an iodine atom, a compound containing a nucleophilic functional group, and a base, in the presence of oxygen. In this case, the compound containing a nucleophilic functional group is represented by the following formula (i), and the carbonate derivative is a linear carbonate derivative represented by the following formula (I), or the compound containing a nucleophilic functional group, is represented by the following formula (ii), bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol TMC and bisphenol Z, and the carbonate derivative is a polycarbonate derivative containing a fragment represented by the following formula (II-1), polycarbonate ester of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol TMC or bisphenol Z, or a cyclic carbonate derivative, represented by the following formula (II-2). At the same time, the base is one or more bases selected from a group consisting of heterocyclic aromatic amine, a non-nucleophilic strong base and an inorganic base, where heterocyclic aromatic amine is pyridine or a pyridine derivative selected from a group consisting of α-picoline, β-picoline, γ-picoline, 2,3-lutidine, 2,4-lutidine, 2,6-lutidine, 3,5-lutidine, 2-chlorpyridine, 3-chlorpyridine and 4-chlorpyridine, where the non-nucleophilic strong base is 1,5,7-triazabicyclo[4.4.0]dec-5-en, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-en, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-en or 1,1,3,3-tetramethylguanidine, and where the inorganic base is alkali metal hydroxide, alkali metal carbonate or alkali metal hydrocarbonate (values for groups in structural formulas are given in the description).

EFFECT: method for producing a carbonate derivative in a safe and effective manner.

(i) R¹–A–H

(ii) H–A–R²–A–H

(I) R¹–A–C(=O)–A–R¹

(II-1) [–A–R²–A–C(=O)–]

6 cl, 1 dwg, 2 tbl, 29 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001]

The present invention relates to a process for producing a carbonate derivative in a safe and efficient manner.

BACKGROUND OF THE INVENTION

[0002]

Linear carbonate among carbonate derivatives is conventionally used as a solvent or the like. In particular, the production of linear carbonate as a non-aqueous solvent for lithium-ion secondary battery electrolyte has been increasing recently. Polycarbonate is produced by the reaction of carbonic acid with a bisphenol compound and is widely used as an engineering plastic with excellent transparency and impact resistance. Urea resin is widely used as a material for glue and tableware. Polydithiocarbonate is acceptable as a stable optical material with low coloration.

[0003]

The carbonate derivative is usually prepared from phosgene and a compound containing a nucleophilic functional group. Phosgene is highly toxic. For example, phosgene readily reacts with water to form hydrogen chloride and has a history of use as a poison gas. In addition, a carbonate derivative is produced by the reaction of carbon monoxide, alcohol and oxygen, but this method has the problem that toxic carbon monoxide must be used under high pressure. Accordingly, various safe methods for producing carbonate ester and polycarbonate have been studied.

[0004]

For example, a method for producing a desired carbonate derivative by subjecting a carbonate ester to an transesterification reaction in the presence of a catalyst is described in Patent Document 1. This method, however, does not provide a fundamental solution, since the problem of obtaining a carbonate derivative as a starting compound remains in this method. This method also has the problems of using an expensive catalyst and the back reaction and side reaction due to residual catalyst.

[0005]

A method for producing a carbonate derivative from an epoxy compound and carbon dioxide in the presence of a catalyst is described in Patent Document 2. In this method, it is not necessary to use phosgene and carbon monoxide. But this method is not suitable for industrial mass production, because it is necessary to use an expensive catalyst and to bring the pressure of carbon dioxide to high levels.

[0006]

The present inventor has developed a method for producing a halogenated carbonate ester by subjecting a halogenated hydrocarbon and an alcohol to an oxidative photoreaction (Patent Document 3) and a method for producing a halogenated formic acid ester, which includes the steps of obtaining a mixture of phosgene by irradiating light with chloroform in the presence of oxygen and reacting the alcohol with the mixture without isolating phosgene (patent document 4).

PRIOR ART DOCUMENTS PATENT DOCUMENTS

[0007]

Patent Document 1: JP H7-10811 A

Patent Document 2: JP 2001-129397 A

Patent Document 3: WO 2014/171367

Patent Document 4: JP 2013-181028 A

NON-PATENT DOCUMENTS

[0008]

Non-Patent Document 1: OKUMA Seiichi et al., The journal of the Japan Society for Analytical Chemistry, Vol. 24, pp. 385–387 (1975)

Non-Patent Document 2: TSURUGI Jitsuo et al., Journal of the Society of Rubber Science and Technology, Japan, Vol. 43, Number 5, pp. 337–346 (1970)

Non-Patent Document 3: Jerzy Herbich et al., J. Photochem. photobiol. A: Chem., 80, pp. 157–160 (1994)

DISCLOSURE OF THE INVENTION

PROBLEMS SOLVED BY THE INVENTION

[0009]

As a rule, phosgene is used to obtain a carbonate derivative, as described above. Even with a production method without using phosgene, there is a problem that another toxic compound or an expensive catalyst must be used, or phosgene must be used to produce the starting compound.

In view of the foregoing, it is an object of the present invention to provide a method for producing a carbonate derivative in a safe and efficient manner.

MEANS FOR SOLVING PROBLEMS

[0010]

The inventor of the present invention has made extensive studies to solve the above problems. As a result, the inventor has carried out the present invention by finding that a carbonate derivative can be obtained in a safe and efficient manner by subjecting a halogenated hydrocarbon compound and a specific compound containing a nucleophilic functional group to photoreactions in the presence of oxygen and a specific base. Since it is generally known that an organic base forms a pigment by photoreaction, plays the role of an antioxidant to capture a radical, and quenches the fluorescence of a compound by a mechanism such as electron transfer, and pyridine is decomposed into glutaconaldehyde or the like by exposure to ultraviolet light (Non-Patent Documents 1 to 3), it is assumed that the organic base is unfavorable for the photoreaction, as in the inventions of the author described in Patent Document 3 and Patent Document 4. On the other hand, it is very surprising that the carbonate derivative is effectively formed by photoreaction in the presence of a specific base.

The following describes the present invention.

[0011]

[1] A process for producing a carbonate derivative, comprising

irradiating with light a composition containing a C _1-4 halogenated hydrocarbon having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a compound containing a nucleophilic functional group, and a base, in the presence of oxygen,

where the compound containing the nucleophilic functional group is represented by the following formula (i), and the carbonate derivative is a linear carbonate derivative represented by the following formula (I), or

a compound containing a nucleophilic functional group is represented by the following formula (ii), and the carbonate derivative is a polycarbonate derivative containing a moiety represented by the following formula (II-1) or a cyclic carbonate derivative represented by the following formula (II-2), and

where the base is one or more bases selected from the group mainly consisting of a heterocyclic aromatic amine, a non-nucleophilic strong base and an inorganic base.

(i) R ¹ –A–H

(ii) H–A–R ² –A–H

(I) R ¹ –A–C(=O)–A–R ¹

(II–1) [–A–R ² –A–C(=O)–]

where

A is O, S or NR ³ where R ³ is an H or C _1-4 alkyl group, or R ³ forms a nitrogen-containing heterocyclic group with R ¹ and N,

R ¹ is a C _6-14 aryl group, a C _4-14 heteroaryl group, or a C _2-24 alkylpolyoxyalkylene group,

R ² is a C _2-10 alkylene group, a C _6-14 arylene group, a C _4-14 heteroarylene group, or a C _2-24 polyoxyalkylene group.

[0012]

[2] The production method according to the above [1], wherein the C _1-4 halogenated hydrocarbon is a C _1-4 polyhalogenated hydrocarbon.

[0013]

[3] The production method according to the above [1], wherein the C _1-4 halogenated hydrocarbon is chloroform.

[0014]

[4] The production method according to any of the above [1] to [3], wherein the heterocyclic aromatic amine is pyridine, picoline, or lutidine.

[0015]

[5] The preparation method according to any of the above [1] - [4], wherein the non-nucleophilic strong base is 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5, 7-triazabicyclo[4.4.0]dec-5-ene, 1.8-diazabicyclo[5.4.0]undec-7-ene, 1.5-diazabicyclo[4.3.0]non-5-ene or 1.1, 3,3-tetramethylguanidine.

[0016]

[6] The production method according to any of the above [1] to [5], wherein the inorganic base is an alkali metal hydroxide, an alkali metal hydrogen carbonate, or an alkali metal carbonate.

[0017]

[7] The production method according to any of the above [1] to [6], in which 0.001 times or more and 1 times or less of the molar amount of the compound containing the nucleophilic functional group, relative to the C _1-4 halogenated hydrocarbon, is used.

[0018]

[8] The preparation method according to any of the above [1] to [7] in which 1.5 times or more and 10 times or less the molar amount of base relative to the compound containing the nucleophilic functional group is used.

[0019]

[9] The production method according to any of the above [1] to [8], wherein the wavelength of the light irradiating the composition is 180 nm or more and 500 nm or less.

THE EFFECT OF THE INVENTION

[0020]

The process of the present invention does not require an expensive catalyst and an extremely toxic compound such as phosgene and carbon monoxide as a starting compound. In this regard, the method of the present invention is industrially very valuable as a technology for producing a suitable carbonate derivative in a safe and efficient manner.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021]

Fig. 1 is a schematic diagram to show an example of a reaction device used in the method of the present invention.

EMBODIMENT OF THE INVENTION

[0022]

In the process for producing a carbonate derivative of the present invention, a composition containing a C _1-4 halogenated hydrocarbon having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a compound containing a nucleophilic functional group, and a specific base, in the presence of oxygen.

[0023]

1. C _1–4 halogenated hydrocarbon

In the reaction of the present invention, the C _1-4 halogenated hydrocarbon can be decomposed by irradiation with light and exposure to oxygen on the halogenated carbonyl or halogenated carbonyl-like compound, and react with a compound containing a hydroxyl group to form a carbonate derivative. Even if a toxic halogenated carbonyl is formed, this halogenated carbonyl reacts immediately with a compound containing a hydroxyl group due to the extremely high reactivity. As a result, there is no leakage of halogenated carbonyl from the reaction mixture or, if leakage of halogenated carbonyl occurs, the amount of leakage is small. For example, there are severe restrictions on the transport of phosgene because phosgene among the halogenated carbonyls is highly toxic; on the other hand, the C _1-4 halogenated hydrocarbon is, of course, not so dangerous. The reaction of the present invention may possibly not be mediated by a halogenated carbonyl or a halogenated carbonyl-like compound, since the reaction proceeds even in the presence of an aqueous solution of an inorganic base, as described below.

[0024]

The C _1-4 halogenated hydrocarbon, which is liquid at atmospheric temperature and atmospheric pressure, is used as an organic solvent or the like in a large amount, but causes environmental pollution such as air pollution and ozone depletion when released into the atmosphere. The present invention is a technology for producing a useful compound by photolysis of a C _1-4 halogenated hydrocarbon and makes a significant contribution to both industry and the environment.

[0025]

A C _1-4 halogenated hydrocarbon is an alkane, alkene or alkyne which has a carbon number of 1 or more and 4 or less and which is substituted by one or more halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom . As described above, the C _1-4 halogenated hydrocarbon can be decomposed by irradiation with light and by exposure to oxygen, and can act similarly to the halogenated carbonyl in the present invention. The C _1-4 halogenated hydrocarbon is preferably a C _1-2 halogenated hydrocarbon and more preferably halogenated methane. When the number of carbon atoms is 2 or more and 4 or less, the C _1-4 halogenated hydrocarbon is preferably an alkene or an alkyne having one or more unsaturations for easier decomposition. In addition, it is preferred that the C _1-4 halogenated hydrocarbon has two or more of the halogen atoms described above. In addition, a C _1-4 polyhalogenated hydrocarbon having two or more of the above-described halogen atoms on the same carbon atom is preferred even if the above-described halogen atom is transferred by decomposition.

[0026]

As specific C _1-4 halogenated hydrocarbon, C _1-4 halogenated alkane, C _2-4 halogenated alkene or C _2-4 halogenated alkyne is preferred, halogenated methane, halogenated ethene or halogenated acetylene is more preferred in terms of ease of formation of halogenated carbonyl-like compounds, polyhalogenated methane, polyhalogenated ethene or polyhalogenated acetylene having two or more of the halogen atoms described above is particularly preferred, and polyhalogenated methane is most preferred. Example C _1-4 halogenated hydrocarbon includes halogenated methane such as dichloromethane, chloroform, dibromomethane, bromoform, iodomethane and diiodomethane; halogenated ethane such as 1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane and 1,1,1,2-tetrachloroethane; halogenated propane such as 1,1,1,3-tetrachloropropane; perhalogenated alkane such as carbon tetrachloride, tetrabromomethane, tetraiodomethane, hexachloroethane and hexabromomethane; perhalogenated ethene such as 1,1,2,2-tetrachloroethene and 1,1,2,2-tetrabromoethene.

[0027]

The C _1-4 halogenated hydrocarbon may be appropriately selected depending on the desired reaction and the desired product. One C _1-4 halogenated hydrocarbon may be used alone, or two or more C _1-4 halogenated hydrocarbons may be used in combination. Preferably, only one C _1-4 halogenated hydrocarbon is used depending on the target compound. A C _1-4 halogenated hydrocarbon having a chlorine group is preferred.

[0028]

The C _1-4 halogenated hydrocarbon used in the process of the present invention may be a C _1-4 halogenated hydrocarbon which was once used as a solvent, for example. It is preferable that such a used C _1-4 halogenated hydrocarbon be purified to some extent for use, because if a large amount of impurities and water is contained, the reaction may be inhibited. For example, it is preferable that water and water-soluble impurities are removed by washing with water, and then the C _1-4 halogenated hydrocarbon is dried with anhydrous sodium sulfate, anhydrous magnesium sulfate, or the like. Excessively large purge, resulting in reduced productivity, is not needed, because even in the presence of water, the reaction can proceed. The water content is preferably 0.5 vol% or less, more preferably 0.2 vol% or less, and even more preferably 0.1 vol% or less. The C _1-4 halogenated hydrocarbon for reuse may contain a decomposition product of the C _1-4 halogenated hydrocarbon.

[0029]

2. Compound containing a nucleophilic functional group

The "compound containing a nucleophilic functional group" in the present invention is a compound that has a nucleophilic functional group containing a nucleophilic oxygen atom, a sulfur atom and/or a nitrogen atom, and which is represented by formula (i) or formula (ii). In some instances, this compound is abbreviated, respectively, as "compound (i) containing a nucleophilic functional group" or "compound (ii) containing a nucleophilic functional group". The compound containing the nucleophilic functional group used in the present invention does not have a fluorine atom as a substituent group; and as a result, the carbonate derivative obtained by the method of the present invention also does not have a fluorine atom as a substituent group. A specific compound containing a nucleophilic functional group is used in the present invention; therefore, the reaction continues until a carbonate derivative is obtained.

[0030]

When the compound (i) containing a nucleophilic functional group is used in the present invention, the resulting carbonate derivative is a linear carbonate represented by formula (I), which is abbreviated as "linear carbonate (I)" in some cases. When a compound containing a hydroxyl group (ii) is used, the resulting carbonate derivative is a polycarbonate derivative containing a moiety represented by formula (II-1), which is abbreviated as "polycarbonate derivative (II-1)" in some cases, or a cyclic carbonate derivative , represented by formula (II-2), which in some cases is abbreviated as "cyclic carbonate derivative (II-2)".

[0031]

Compound (i) containing a nucleophilic functional group and compound (ii) containing a nucleophilic functional group used in the production method of the present invention as a starting compound, and a linear carbonate derivative (I), a polycarbonate derivative (II-1) and a cyclic carbonate derivative (II–2) as the target compound are described below.

(i) R ¹ –A–H

(ii) H–A–R ² –A–H

(I) R ¹ –A–C(=O)–A–R ¹

(II–1) [–A–R ² –A–C(=O)–]

[0032]

[0033]

where

A is O, S or NR ³ where R ³ is an H or C _1-4 alkyl group, or R ³ forms a nitrogen-containing heterocyclic group with R ¹ and N,

R ¹ is a C _6-14 aryl group, a C _4-14 heteroaryl group, or a C _2-24 alkylpolyoxyalkylene group,

R ² is a C _2-10 alkylene group, a C _6-14 arylene group, a C _4-14 heteroarylene group, or a C _2-24 polyoxyalkylene group.

[0034]

In this specification, a halogenated hydrocarbon having 1 or more and 4 or less carbon atoms is referred to as "C _1-4 halogenated hydrocarbon". Other groups and compounds are described in a similar way.

[0035]

R ³ in the compound (i) containing a nucleophilic functional group is preferably H. The nitrogen-containing heterocyclic group formed by R ¹ , R ³ and N may be a non-aromatic nitrogen-containing heterocyclic group or an aromatic nitrogen-containing heterocyclic group. An example of a non-aromatic nitrogen-containing heterocyclic group includes pyrrolidinyl and piperidinyl. An example of an aromatic nitrogen-containing heterocyclic group includes pyrrolyl, imidazolyl and pyrazole.

[0036]

The hydrogen atom in the C _6-14 aryl group may be replaced by a chlorine atom, a bromine atom, an iodine atom, or a C _1-8 alkyl group.

[0037]

C _4-14 heteroaryl group means an aromatic heterocyclic group having one or more nitrogen atoms, oxygen atoms or sulfur atoms. An example of a heterocyclic group is a five-membered heteroaryl group such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl and thiadiazole; a six-membered heteroaryl group such as pyridinyl, pyrazinyl, pyrimidinyl and pyridazinyl; a fused aromatic heterocyclic group such as indolyl, isoindolyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl and chromenyl, preferably a C _4-14 heteroaryl group containing a nitrogen atom, and more preferably pyridinyl.

[0038]

The C _2-24 alkyl polyoxyalkylene group is preferably a group represented by the formula: -(Q ^H O) _m R ^H where Q ^H is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, - CH ₂ CH(CH ₃ )– or –CH ₂ CH ₂ CH ₂ CH ₂ –, R ^H is –CH ₃ or –CH ₂ CH ₃ , m is an integer equal to 1 or more and 20 or less. When m is 2 or more, Q ^H may consist of only one type, or may consist of more than one type. When Q ^H can be composed of multiple types, the arrangement of multiple Q ^H types can be random or block.

[0039]

The C _2-24 polyoxyalkylene group is preferably a group represented by the formula: -(Q ^H O) _m Q ^H -.

[0040]

The C _2-10 alkylene group may be linear, branched, or cyclic. The C _2-10 alkylene group is preferably a C _2-6 alkylene group, and more preferably a C _2-4 alkylene group. The C _2-10 alkylene group is preferably an ethylene group optionally substituted with one or two C _1-4 alkyl groups, more preferably an ethylene group optionally substituted with one or two C _1-2 alkyl groups, and even more preferably an ethylene group, optionally substituted with one or two methyl groups, from the point of view of the ease of obtaining a cyclic carbonate. The above described ethylene group substituted with an alkyl group can also be described as a 1,2-alkylene group.

[0041]

C _6-14 arylene group, C _4-14 heteroarylene group and C _2-24 polyoxyalkylene group are respectively divalent organic groups corresponding to C _6-14 aryl group, C _4-14 heteroaryl group and C _2-24 alkylpolyoxyalkylene group.

[0042]

An example of a compound (i) containing a nucleophilic functional group includes a compound (i) containing a hydroxyl group, a compound (i) containing a thiol group, and a compound (i) containing an amino group. An example of compound (i) containing a hydroxyl group includes phenol and its derivative, including phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-methylphenol, 3 -methylphenol and 4-methylphenol; C _3-10 cycloalkanol, such as cyclohexanol; benzyl alcohol and its derivative, including benzyl alcohol and 2,6-benzyl alcohol; an alkylene glycol mono(C _1-4 alkyl) ether such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; an oligoalkylene glycol mono(C _1-4 alkyl) ether such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether and tetraethylene glycol monomethyl ether.

[0043]

An example of compound (i) containing a thiol group includes thiophenol and its derivative, including thiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 2-methylthiophenol, 3 -methylthiophenol and 4-methylthiophenol; C _3-10 cycloalkanethiol such as cyclohexanethiol; benzylmercaptan and its derivative, including benzylmercaptan, 2-chlorobenzylmercaptan, 4-chlorobenzylmercaptan and 4-methoxybenzylmercaptan; a simple mono(C _1-4 alkyl) thioether of 1,2-ethanedithiol such as HSCH ₂ CH ₂ SCH ₃ , HSCH ₂ CH(CH ₃ )SCH ₃ and HSCH(CH ₃ )CH ₂ SCH ₃ ; mono(C _1-4 alkyl) thioether of oligo(1,2-ethanedithiol)alkylene glycol, such as di(1,2-ethanedithiol) monomethyl thioether, tri(1,2-ethanedithiol) monomethyl thioether, and monomethyl thioether tetra(1,2-ethanedithiol).

[0044]

An example of compound (i) containing an amino group includes aniline and its derivative, including aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-methylaniline, 3- methylaniline and 4-methylaniline; C _3-10 cycloalkylamine, such as cyclohexylamine; a heterocyclic amine such as piperazine and piperidine; benzyl alcohol and its derivative such as benzylamine, 4-(aminomethyl)benzylamine, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-bromobenzylamine, 3-bromobenzylamine, 4-bromobenzylamine and 4-tert-butylbenzylamine; an alkylene glycol mono(C _1-4 alkyl) ether such as N-methylethylenediamine, N,N-dimethylethylenediamine, N-methylpropylenediamine and N,N-dimethylpropylenediamine; N-mono(C _1-4 alkyl) oligoethylenediamine or N,N-di(C _1-4 alkyl) oligoethylenediamine such as N-methyldiethylenetriamine, N,N-dimethyldiethylenetriamine, N-methyltriethylenetetramine, N,N-dimethyltriethylenetetramine, N- methyltetraethylenepentamine and N,N-dimethyltetraethylenepentamine.

[0045]

Only one compound (i) containing a nucleophilic functional group may be used alone, or two or more compounds (i) containing a nucleophilic functional group may be used in combination. For example, by using two compounds (i) containing nucleophilic functional groups, an asymmetric linear carbonate derivative can be synthesized. However, it is preferred that only one compound (i) containing a nucleophilic functional group be used.

[0046]

Compound (ii) containing a nucleophilic functional group is preferably a compound represented by the following formulas (ii-1) and (ii-2).

(ii–1) H–A–R ²¹ –A–H

(ii–2) H–A–R ²² –R ²³ –R ²⁴ –A–H

where

A has the same meaning as above.

R ²¹ is a C _2-10 alkylene group, a C _6-14 arylene group, or a C _4-14 heteroarylene group,

R ²² and R ²⁴ are independently a C _6-14 arylene group or a C _4-14 heteroarylene group,

R ²³ is a C _1-10 alkylene group.

[0047]

When the compound (ii) containing a hydroxy group is used as a starting compound, a polycarbonate derivative (II-1) or a cyclic carbonate derivative (II-2) can be obtained. In particular, when the number of carbon atoms in the main chain in R ² is 2 or 3, and a stable structure such as a five-membered ring and a six-membered ring is formed with a carbonate ester group (–O–C(=O)–O–), carbonate dithioester group (–S–C(=O)–S–) or carbamide group (–NH–C(=O)–NH–), – cyclic carbonate derivative is mainly formed. In particular, when the C _2-10 alkylene group, the C _6-14 arylene group, and the C _4-14 heteroarylene group in the compound (ii-1) containing the nucleophilic functional group are, respectively, 1,2-C _2-10 alkylene group, 1,2–C _6–14 arylene group, and 1,2–C _4–14 heteroarylene group, cyclic carbonate is mainly formed. When the number of carbon atoms in the main chain in R ² is 4 or more, a chemically more stable compound is preferably formed between the cyclic carbonate derivative and the polycarbonate derivative depending on the reaction conditions or the like.

[0048]

An example of a 1,2-arylene group includes 1,2-naphthalenylene, 1,8-naphthalenylene and 2,3-naphthalenylene having the following structure in addition to the 1,2-phenylene group and 1,2-biphenylene. The same applies to the 1,2–(C _2–10 alkylene) group and the 1,2–(C _4–14 heteroarylene) group.

[0049]

[0050]

An example of a compound (ii) containing a nucleophilic functional group includes a compound (ii) containing a hydroxyl group, a compound (ii) containing a thiol group, and a compound (ii) containing an amino group. An example of compound (ii) containing a hydroxyl group includes a glycol compound such as 1,2-propanediol, 1,2-ethanediol and 1,4-butanediol; a dihydroxybenzene compound such as catechol and resorcinol; a dihydroxyheteroaryl compound such as 4,6-dihydroxy-2-methylpyrimidine and 3,6-dihydroxy-4-methylpyridazine; a bisphenol compound such as bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol TMC, and bisphenol Z.

[0051]

For example, when using bisphenol A as the compound (ii) containing a hydroxyl group, a polycarbonate ester represented by the following formula is obtained.

[0052]

[0053]

An example of compound (ii) containing a thiol group includes a C _1-4 alkylene dithiol compound such as 1,2-propanedithiol, 1,2-ethanedithiol and 1,4-butanedithiol; a benzene dithiol compound such as 1,2-benzenedithiol and 1,3-benzenedithiol; a heteroaryldithiol compound such as 2-methylpyrimidine-4,6-dithiol and 4-methylpyridazine-3,6-dithiol; a bisthiophenol compound such as 4,4'-thiobisbenzenethiol, 2,2-bis(4-mercaptophenyl)propane, 1,1-bis(4-mercaptophenyl)-1-phenylethane, 2,2-bis(4-mercaptophenyl)butane , bis(4-mercaptophenyl)diphenylmethane, 1,1-bis(4-mercaptophenyl)ethane, bis(4-mercaptophenyl)methane, 1,1-bis(4-mercaptophenyl)-3,3,5-trimethylcyclohexane and 1, 1-bis(4-mercaptophenyl)cyclohexane.

[0054]

An example of compound (ii) containing an amino group includes a C _1-4 alkylenediamine compound such as 1,2-propylenediamine, 1,3-propylenediamine, 1,2-ethylenediamine, and 1,4-butylenediamine; a phenylenediamine compound such as 1,2-phenylenediamine and 1,4-phenylenediamine; a heteroaryldithiol compound such as 4,6-diamino-2-methylpyrimidine and 3,6-diamino-4-methylpyridazine; bisaminobenzene compound such as 2,2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)-1-phenylethane, 2,2-bis(4-aminophenyl)butane, bis(4-aminophenyl) diphenylmethane, 1,1-bis(4-aminophenyl)ethane, bis(4-aminophenyl)methane, 1,1-bis(4-aminophenyl)-3,3,5-trimethylcyclohexane and 1,1-bis(4-aminophenyl) )cyclohexane.

[0055]

The use of a C _1-4 halogenated hydrocarbon and a compound containing a nucleophilic functional group is not particularly limited as long as the reaction proceeds and the target product can be obtained, and for example, even when 1× molar amount of the compound containing a nucleophilic functional group is used. , relative to the number of moles C _1–4 of the halogenated hydrocarbon, the reaction proceeds. The molar ratio of a compound containing a nucleophilic functional group to a C _1–4 halogenated hydrocarbon, i.e. [compound containing a nucleophilic functional group] / [C _1-4 halogenated hydrocarbon] is preferably 0.001 or more and 1 or less in terms of reaction efficiency and reaction time. The molar ratio is more preferably 0.01 or more, even more preferably 0.1 or more, and more preferably 0.8 or less, even more preferably 0.5 or less. When the molar ratio is too large, the amount of the compound containing the nucleophilic functional group becomes proportionally large, and the amount of the unreacted compound containing the nucleophilic functional group increases. On the other hand, when the molar ratio is too small, the amount of unreacted C _1-4 halogenated hydrocarbon increases, and there may be leakage of halogenated carbonyl from the reaction system. When the C _1-4 halogenated hydrocarbon is liquid at ordinary temperature and ordinary pressure and can be used as a solvent, the ratio of the compound containing the nucleophilic functional group to the C _1-4 halogenated hydrocarbon may be 1 mg/mL or more and 500 mg/mL or less.

[0056]

3. Foundation

One or more bases selected from the group mainly consisting of a heterocyclic aromatic amine, a non-nucleophilic strong base and an inorganic base are used in the method of the present invention. The reaction can continue as long as the polycarbonate derivative is formed with the base.

[0057]

Heterocyclic aromatic amine means a compound having at least one heterocyclic ring and at least one functional amino group. An example of such a heterocyclic aromatic amine includes pyridine and its derivative, including pyridine, α-picoline, β-picoline, γ-picoline, 2,3-lutidine, 2,4-lutidine, 2,6-lutidine, 3,5- lutidine, 2-chloropyridine, 3-chloropyridine and 4-chloropyridine.

[0058]

"Non-nucleophilic strong base" means a base in which the nucleophilicity of the lone pair on the nitrogen atom is weak due to steric obstruction, and whose basicity (pK _BH+ ) in acetonitrile is 20 or more. An example of such a non-nucleophilic strong base includes 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, pK _BH+ : 25.98), 7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-ene (MTBD, pK _BH+ : 25.44), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, pK _BH+ : 24.33), 1,5-diazabicyclo[4.3. 0]non-5-ene (DBN, pK _BH+ : 23.89) and 1,1,3,3-tetramethylguanidine (TMG, pK _BH+ : 23.30).

[0059]

An example of an inorganic base includes an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; an alkaline earth metal hydroxide such as calcium hydroxide; an alkali metal carbonate such as sodium carbonate and potassium carbonate; an alkaline earth metal carbonate such as calcium carbonate; an alkali metal hydrogen carbonate such as sodium hydrogen carbonate.

[0060]

The inorganic base may be pulverized just prior to use to be added to the reaction mixture, or preferably an aqueous solution thereof is added. The concentration of the aqueous solution of the inorganic base may be adjusted accordingly, and, for example, may be adjusted to 0.05 g/ml or more and 2 g/ml or less. An aqueous solution of an inorganic base is used to decompose phosgene. In particular, phosgene is decomposed by water into carbon dioxide and hydrogen chloride, and the hydrogen chloride can be neutralized with an inorganic base. Since the inventor believed that the reaction of the present invention proceeds through phosgene, it is noteworthy that the reaction of the present invention proceeds even when an aqueous solution of an inorganic base is used, as in the example described below. In addition, since the reaction of the present invention proceeds even when an aqueous solution of an inorganic base is used, the reaction can proceed without passing through phosgene.

[0061]

One base may be used alone, or two or more bases may be used in combination.

[0062]

The use of a base may be adjusted accordingly, provided that the reaction proceeds successfully, and for example, the ratio to a compound containing a nucleophilic functional group may be adjusted in moles to 1.5 times or more and 10 times or less. When more base is used, the output usually becomes larger; therefore, the mole ratio is preferably 2.0 times or more, more preferably 3.0 times or more, and even more preferably 4.0 times or more.

[0063]

4. Reaction conditions

The method of the present invention includes the step of irradiating with light a composition containing a C _1-4 halogenated hydrocarbon, a compound containing a nucleophilic functional group, and a base, in the presence of oxygen.

[0064]

The mixing method of the C _1-4 halogenated hydrocarbon, the compound containing the nucleophilic functional group, and the base is not particularly limited. For example, the total amount of each compound may be premixed in the reaction vessel, the compounds may be added in multiple portions, or added continuously at any rate. When one or both of the C _1-4 halogenated hydrocarbon and the nucleophilic functional group-containing compound are not liquid at ordinary temperature and ordinary pressure, a solvent can be used which can properly dissolve the starting compounds and which does not inhibit the reaction of the present invention. An example of such a solvent includes an aliphatic hydrocarbon solvent such as n-hexane; aromatic hydrocarbon solvent such as benzene, toluene, xylene and chlorobenzene; an ethereal solvent such as diethyl ether, tetrahydrofuran and dioxane; and a nitrile solvent such as acetonitrile.

[0065]

The source of oxygen may be a gas containing oxygen and, for example, air or purified oxygen may be used. Purified oxygen can be mixed with inert gas such as nitrogen and argon for use. It is preferable to use air from the point of view of cost and ease. The oxygen content of the air used as the oxygen source is preferably about 15 vol% or more and about 100 vol% or less from the viewpoint of high efficiency of decomposition of C _1-4 halogenated hydrocarbon by light irradiation. The oxygen content can be appropriately determined depending on the kind of C _1-4 halogenated hydrocarbon or the like. For example, when a C _1-4 chlorohydrocarbon compound such as dichloromethane, chloroform and tetrachlorethylene is used as the C _1-4 halogenated hydrocarbon, the oxygen content is preferably 15 vol% or more and 100 vol% or less. When a C _1-4 bromohydrocarbon compound such as dibromomethane and bromoform is used, the oxygen content is preferably 90 vol% or more and 100 vol% or less. Even when oxygen is used or the oxygen content is 100% by volume, the oxygen content can be controlled within the above-described range by adjusting the flow rate of oxygen into the reaction system. The method of supplying the oxygen-containing gas is not particularly limited, and the gas may be supplied to the reaction system from an oxygen cylinder provided with a flow controller or from an oxygen generating device.

[0066]

The term "in the presence of oxygen" means any one of the states in which each compound described above is in contact with oxygen and the state in which oxygen is present in the composition described above. The reaction of the present invention can be carried out in an oxygen-containing gas stream, but it is preferable to supply the oxygen-containing gas to the composition by sparging from the point of view of high product yield.

[0067]

The amount of oxygen-containing gas may be appropriately determined depending on the amount of C _1-4 halogenated hydrocarbon or the shape of the reaction vessel. For example, the amount of gas supplied to the reaction vessel per minute relative to the C _1-4 halogenated hydrocarbon in the reaction vessel is preferably 5 times or more by volume. The ratio is more preferably 25 times or more by volume, and even more preferably 50 times or more by volume. The upper limit of the ratio is not particularly limited, and the ratio is preferably 500 times or less by volume, more preferably 250 times or less by volume, and even more preferably 150 times or less by volume. The amount of oxygen supplied to the reaction vessel per minute, relative to the C _1-4 hydrocarbon compound in the reaction vessel, may be 5 times or more by volume and 25 times or less by volume. When the amount of gas is too large, the C _1-4 hydrocarbon compound may volatilize, but when the amount is too small, the reaction may be hindered.

[0068]

The light irradiating the composition is preferably light containing short wavelength light, more preferably light containing ultraviolet light, and preferably light containing light, in particular having a wavelength of 180 nm or more and 500 nm or less. The wavelength of light can be appropriately determined depending on the kind of C _1-4 halogenated hydrocarbon, and is more preferably 400 nm or less, and even more preferably 300 nm or less. When the irradiating light contains light of the wavelength range described above, the C _1-4 halogenated hydrocarbon undergoes oxidative photochemical degradation in an efficient manner.

[0069]

The light irradiation means is not particularly limited as long as the light of the above-described wavelength can be emitted by the means. An example of a light source having such a wavelength range includes sunlight, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, a metal halide lamp, and an LED lamp. A low pressure mercury lamp is preferably used in terms of reaction efficiency and cost.

[0070]

Conditions such as irradiation light intensity, irradiation time, or the like can be appropriately determined depending on the kind and amount of raw materials used, and for example, the irradiation light intensity is preferably 10 μW/cm ² or more and 500 μW/cm ² or less. The intensity of the irradiating light is more preferably 100 μW/cm ² or less, and even more preferably 40 μW/cm ² or less. The irradiation time is preferably 0.5 hours or more and 10 hours or less, more preferably 1 hour or more and 6 hours or less, and even more preferably 2 hours or more and 4 hours or less. The light irradiation method is also not particularly limited, and any methods can be selected. For example, the light irradiation may be continuous from the beginning of the reaction until the completion of the reaction, the periods of light irradiation and its termination may be alternately repeated, and the light irradiation may occur from the start of the reaction only for a predetermined time. Preferably continuous light irradiation from the beginning of the reaction until the completion of the reaction.

[0071]

The temperature during the reaction is not particularly limited and can be suitably adjusted, and, for example, can be adjusted to 0°C or higher and 50°C or lower. The temperature is more preferably 10°C or higher, even more preferably 20°C or higher, and more preferably 40°C or lower, even more preferably 30°C or lower.

[0072] An example of a reaction device used in the production method of the present invention is a reaction vessel provided with a light irradiation means. The reaction device may be provided with a stirrer and temperature control means. One of the embodiments of the reaction device used in the production method of the present invention is shown in Fig.1. The reaction apparatus shown in FIG. 1 has a light irradiation means 1 in a tubular reaction vessel 6. The starting compounds described above are added to the tubular reaction vessel 6, and light is irradiated using the light irradiation means 1 while an oxygen-containing gas is supplied into the tubular reaction vessel 6, or a gas containing oxygen is blown into the composition to cause bubbling (not shown in the figure) to carry out the reaction. When the light irradiation means 1 is covered with a jacket 2 or the like, it is preferable that the jacket is composed of a material through which short-wavelength light penetrates. Irradiation with light may occur outside the reaction vessel. In such a case, the reaction vessel consists of a material through which short-wavelength light penetrates. The material through which short-wavelength light penetrates is not particularly limited as long as the effect of the present invention is not inhibited, and is preferably quartz glass.

[0073]

The product resulting from the reaction can be purified in a conventional manner. An example of such a purification method includes distillation, removal of starting compounds under reduced pressure, column chromatography, liquid separation, extraction, washing, and recrystallization.

[0074]

When a compound containing a hydroxyl group, a compound containing a thiol group, or a compound containing an amino group is used as a starting compound containing a nucleophilic functional group, a carbonate derivative having, respectively, a carbonate ester group (–O–C(=O) –O–), a carbonate dithioester group (–S–C(=O)–S–), or a urea group (–NH–C(=O)–NH–). When a compound containing a hydroxyl group and a compound containing an amino group are used in combination, a carbonate derivative having a urethane group (–O–C(=O)–NH–) is obtained. When a compound containing a thiol group and a compound containing an amino group are used in combination, a carbonate derivative having a thiourethane group (–S–C(=O)–NH–) is obtained.

[0075]

The linear carbonate derivative (I) obtained by the method of the present invention can be used as a non-aqueous solvent or the like. For example, linear carbonate (I) can be used as an electrolyte solvent for a lithium-ion secondary battery. Polycarbonate (II) can be used as an excellent engineering plastic.

[0076]

The present application claims benefit as of the filing date over Japanese Patent Application No. 2017-97681, filed May 16, 2017. The entire content of Japanese Patent Application No. 2017-97681, filed May 16, 2017, is incorporated herein by reference.

EXAMPLES

[0077]

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is in no way limited to the following examples, and it is possible to carry out the present invention in accordance with these examples with further appropriate modifications within the foregoing descriptions and the following descriptions. Such a modified embodiment is also within the technical scope of the present invention.

[0078]

Comparative Example 1 Synthesis of Dimethyl Carbonate

A quartz glass jacket with a diameter of 30 mm was inserted into a tubular reaction vessel having a diameter of 42 mm and a volume of 100 ml, and a low pressure mercury lamp (“UVL20PH–6” manufactured by SEN Light, 20 W, Ø24 × 120 mm) was then inserted into a jacket of quartz glass to collect the reaction system. A schematic representation of the reaction system is shown in Fig.1. Purified chloroform (20 ml), methanol (0.405 ml, 10 mmol) and 5 moles of pyridine (4.03 ml) relative to the amount of methanol were added to the reaction vessel. The mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. The reaction mixture was analyzed by ¹ H-NMR after 3 h; as a result, it was confirmed that the yield of dimethyl carbonate as the target compound was almost 1.6%.

[0079]

Comparative Example 2

The reaction was carried out in the same manner as in Comparative Example 1 above, except that ethanol was used instead of methanol. It was not confirmed that the reaction proceeded even after 3 hours. Considering this result, along with the result of Comparative Example 1, it becomes obvious that the method of the present invention is difficult to apply to monovalent alcohol.

[0080]

Example 1 Synthesis of diphenyl carbonate

(1) Use of pyridine as a base

The reaction was carried out similarly to Comparative Example 1 above, except that phenol (0.94 g, 10 mmol) was used instead of methanol, the amount of pyridine used per mole was adjusted to 3.5 times the amount of phenol, and the reaction time was 2 hours After the reaction, water and dichloromethane were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The solid thus obtained was recrystallized using dichloromethane and n-hexane to give diphenyl carbonate as a white solid title compound (yield of isolated product: 61%).

[0081]

(2) Use of pyridine as a base

Diphenyl carbonate as a white solid title compound was obtained (yield of isolated product: more than 99%) analogously to Example 1(1) above, except that 5 times the molar amount of pyridine relative to phenol was used and the reaction time was 1 hour.

[0082]

(3) Using 2,6-lutidine as a base

Diphenyl carbonate as the target compound was obtained (yield of isolated product: 60%) in the same manner as in Example 1(1) above, except that 2,6-lutidine was used instead of pyridine and the reaction time was 1 hour.

[0083]

(4) Use of carbon tetrachloride

The reaction was carried out analogously to Example 1(1) described above, except that carbon tetrachloride (25 ml) and 5 times the molar amount of pyridine relative to phenol were used instead of chloroform. After the reaction, water and dichloromethane were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The solid thus obtained was recrystallized using dichloromethane and n-hexane to give diphenyl carbonate as a white solid title compound (yield of isolated product: 69%).

[0084]

Comparative Example 3

The reaction was carried out analogously to Example 1(2) above, except that triethylamine was used instead of pyridine. However, only a small amount of black tar was isolated, and diphenyl carbonate could not be isolated as the target compound. As just described, when triethylamine was used as the organic base, diphenyl carbonate could not be obtained; on the other hand, diphenyl carbonate could be obtained with a yield of more than 99% only by replacing the organic base from triethylamine with pyridine.

[0085]

Example 2: Synthesis of bis(pentachlorophenyl)carbonate

The reaction was carried out in the same manner as in Comparative Example 1 above, except that pentachlorophenol (1.13 g, 5 mmol) was used instead of methanol. After the reaction, methanol was added to the suspended reaction mixture to form a white solid. The resulting white solid was collected by suction filtration as the title compound, bis(pentachlorophenyl)carbonate (isolated product yield: 72%).

[0086]

Example 3: Synthesis of 1,3-benzodioxol-2-one

Purified chloroform (20 ml), catechol (1.1 g, 10 mmol) and 5 times the molar amount of pyridine (4.03 ml) relative to catechol were added to the reaction vessel described above and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 2 hours, water and dichloromethane were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The solid thus obtained was recrystallized using dichloromethane and n-hexane to give the desired 1,3-benzodioxol-2-one (yield of isolated product: more than 99%).

[0087]

Example 4 Synthesis of Ethylene Carbonate

The reaction was carried out analogously to Example 3 above, except that ethylene glycol (0.28 ml, 10 mmol) was used instead of catechin. After the reaction, the reaction mixture was analyzed by ¹ H-NMR to confirm the formation of the desired ethylene carbonate (yield of isolated product: 44%).

[0088]

Example 5 Synthesis of Bisphenol A Polycarbonate

Purified chloroform (20 ml), bisphenol A (2.28 g, 10 mmol) and 5 times the molar amount of pyridine (4.03 ml) relative to bisphenol A were added to the reaction vessel described above and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. Since the stirring rod could not rotate due to the increased viscosity of the reaction mixture after 40 minutes, methanol (30 ml) was added to the reaction mixture, irradiated with ultrasonic waves, and the reaction mixture was suction filtered. The resulting solid was washed with methanol and then dried under vacuum to give a white solid. The white solid was analyzed by ¹ H-NMR; as a result, it was confirmed that the target bisphenol A polycarbonate could be obtained with a yield of more than 99%.

The resulting bisphenol A polycarbonate was analyzed by gel permeation chromatography (GPC) under the following conditions to determine the molecular weight. The results are shown in Table 1.

Device: High Efficiency GPC Device ("HLC-8320GPC" by Tosoh Corporation)

Column: Ultra-high molecular weight column ("TSKgel GMHHR-H×2" manufactured by Tosoh Corporation)

Mobile phase: chloroform; Flow rate: 1.0 ml/min

Furnace temperature: 40°C; Concentration: 0.3% w/v

Injection amount: 100 µl

Molecular weight standard: polystyrene

Detector: RI

[0089]

Table 1.

Mn Mw Mw/Mn 23000 52000 2.3

[0090]

From the result shown in Table 1, it was found that the polycarbonate ester synthesized by the method of the present invention has a sufficiently high molecular weight, and the molecular weight distribution is relatively narrow.

[0091]

Example 6: Synthesis of bis(triethylene glycol monomethyl ether) carbonate

The reaction was carried out in the same manner as in Comparative Example 1 above, except that triethylene glycol monomethyl ether (1.64 g, 10 mmol) was used instead of methanol. After the reaction, water and a mixed solvent of dichloromethane:ethyl acetate=1:1 were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to give bis(triethylene glycol monomethyl ether) carbonate as a brown oily title compound (yield of isolated product: more than 99%).

[0092]

Example 7 Synthesis of Tetraethylene Glycol Polycarbonate

The reaction was carried out in the same manner as in Comparative Example 1 above, except that tetraethylene glycol (1.50 g, 10 mmol) was used instead of methanol, and the reaction time was 2 hours. After the reaction, water and ethyl acetate were added to the reaction mixture, and the organic phase and aqueous phase was separated. The organic phase was washed three times with salt water. The organic phase was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain tetraethylene glycol polycarbonate as a brown oily title compound (yield of isolated product: more than 99%).

¹ H–NMR (400 MHz, CDCl ₃ ) δ 4.28 (t, J=4.8 Hz, –CO ₂ CH ₂ –), 3.73 (t, J=4.8 Hz, –CH ₂ – ), 3.68–3.63 (m, –CH ₂ –);

FAB-MS: m/z 519, 739, 958;

IR (KBr): 2955, 2891, 1740, 1459, 1396, 1354, 1271, 1100, 1029, 950, 864, 791 cm– ¹

[0093]

Example 8: Photoinduced copolymerization of bisphenol A and hexamethylenediamine

Purified chloroform (30 ml), bisphenol A (0.685 g, 3 mmol), hexamethylenediamine (0.412 g, 3 mmol) and aqueous sodium hydroxide solution (20 ml, 100 mmol) were added to the above reaction vessel, and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 2 hours, water and dichloromethane were added to the reaction mixture. The resulting precipitate was obtained by filtration, washed with methanol and dried under vacuum at 70°C. The organic phase and the aqueous phase of the filtrate were separated. The organic phase was concentrated under reduced pressure. The residue thus obtained was washed with methanol and then dried under vacuum at 70° C. to obtain a light orange powder (yield: 39%). The resulting powder was analyzed by ¹ H-NMR and IR, as a result of which the formation of the target copolymer was confirmed.

As described above, even when an aqueous solution of an inorganic base is used, a carbonate derivative can be obtained. Since an aqueous solution of an inorganic base was used to decompose phosgene, the above experimental result is by no means expected, and it is believed that the reaction of the present invention can proceed without passing through phosgene.

Since the initially obtained precipitate was insoluble in the solvent and the powder obtained from the filtrate was soluble in DMSO or the like, the molecular weights of both powders may be different.

[0094]

Example 9: Synthesis of Bisphenyl Carbonate

Purified chloroform (20 ml), phenol (0.941 g, 10 mmol) and aqueous sodium hydroxide solution (20 ml, 100 mmol) were added to the above reaction vessel, and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 3 hours, water and dichloromethane were added to the reaction mixture. The organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure at 70° C. to give a light orange solid (yield: 55%). The resulting solid was analyzed by ¹ H-NMR, and the formation of the title compound was confirmed.

[0095]

Example 10 Synthesis of Dicyclohexyl Carbonate

A light yellow liquid was obtained (yield: 13%) analogously to Example 9 above, except that cyclohexanol (1.06 ml, 10 mmol) was used instead of phenol. The resulting liquid was analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0096]

Example 11: Synthesis of bis(4-tert-butylphenyl)carbonate

Purified chloroform (20 ml), 4-tert-butylphenol (1.53 g, 10 mmol), aqueous sodium carbonate solution (20 ml, 50 mmol) and pyridine (0.202 ml, 5 mmol) were added to the above reaction vessel and the mixture stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 3 hours, chloroform and water were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure at 70°C. The residue thus obtained was recrystallized to give a light orange powder (yield: 57.0%). The resulting powder was analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0097]

Example 12: Synthesis of bis(4-methoxyphenyl)carbonate

A brown solid was obtained (yield: 60%) similarly to Example 9 above, except that 4-methoxyphenol (10 mmol) was used instead of phenol and 30 ml of chloroform was used. The resulting solid was analyzed by ¹ H-NMR and IR, whereby the formation of the target compound was confirmed.

[0098]

Example 13: Synthesis of bis(4-nitrophenyl)carbonate

A white powder was obtained (yield: 5%) in the same manner as in Example 9 above, except that 4-nitrophenol (1.391 g, 10 mmol) was used instead of phenol and 30 ml of chloroform was used, and the reaction time was 2 hours. The resulting powder was analyzed with using ¹ H-NMR and IR, which confirmed the formation of the target compound.

[0099]

Example 14 Synthesis of Bisphenol A Polycarbonate

Purified chloroform (20 ml), bisphenol A (1.14 g, 5 mmol) and aqueous sodium hydroxide solution (100 mmol, 20 ml) were added to the above reaction vessel, and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 2 hours the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. Then, chloroform and methanol were added thereto, and the solvent was removed by decantation, the residue was dried at 70°C under reduced pressure to obtain a white solid (yield: 79%). The resulting solid was analyzed by ¹ H-NMR, and the formation of the title compound was confirmed.

The molecular weight of the resulting bisphenol A polycarbonate was determined under conditions similar to Example 5 above. The results are shown in Table 2.

[0100]

table 2

Mn Mw Mw/Mn 4600 15200 3.3

[0101]

From the result shown in Table 2, it was found that the polycarbonate ester synthesized by the method of the present invention has a sufficiently high molecular weight, and the molecular weight distribution is relatively narrow.

[0102]

Example 15 Synthesis of Dihexyl Carbonate

The reaction was carried out analogously to Example 9 above, except that 1-hexanol (1.25 ml, 10 mmol) was used instead of phenol. The reaction mixture was dried with anhydrous sodium sulfate. Dichloromethane (0.64 ml, 10 mmol) was added thereto as an internal standard, and the reaction mixture was directly analyzed by ¹ H-NMR, whereby the formation of the title compound was confirmed (yield: >99%).

[0103]

Example 16 Synthesis of Dipentyl Carbonate

The reaction was carried out analogously to Example 9 described above, except that 1-pentanol (10 mmol) was used instead of phenol. The reaction mixture was dried with anhydrous sodium sulfate. Dichloromethane (0.64 ml, 10 mmol) was added thereto as an internal standard, and the reaction mixture was directly analyzed by ¹ H-NMR, whereby the formation of the title compound was confirmed (yield: 12%).

[0104]

Example 17: Synthesis of 1,3-diphenylurea

Purified chloroform (20 ml), aniline (0.93 g, 10 mmol) and aqueous sodium hydroxide solution (NaOH: 4 g, 20 ml) were added to the above reaction vessel, and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 2 hours, dichloromethane and water were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The black solid thus obtained was recrystallized using dichloromethane and n-hexane to obtain a black powder (yield by mass: 0.13 g, yield: 12%). The resulting solid was analyzed by ¹ H-NMR, and the formation of the title compound was confirmed.

[0105]

Example 18: Synthesis of 1,3-dicyclohexylurea

A white powder was obtained (yield by mass: 0.69 g, yield: 62%) similarly to Example 17 above, except that cyclohexylamine (1.17 ml, 10 mmol) was used instead of aniline, the reaction time was 3 hours, and after the reaction, a precipitate formed by adding hexane and water was obtained by filtration and dried under vacuum. The resulting powder was analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0106]

Example 19: Synthesis of 1,3-dibenzylurea

A light brown powder was obtained as the title compound (yield by mass: 0.78 g, yield: 65%) as in Example 17 above, except that benzylamine (1.07 g, 10 mmol) was used instead of aniline, time reaction was 5 hours, and after the reaction, hexane and water were added to the reaction mixture to obtain a precipitate by filtration, and the precipitate was dried under vacuum. The resulting powder was analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0107]

Example 20: Synthesis of 1,3-dihexylurea

A white powder was obtained (yield by mass: 0.58 g, yield: 51%) as in Example 17 above, except that 1-hexylamine (1.01 g, 10 mmol) was used instead of aniline, the reaction temperature was 10° C, and the reaction time was 3 hours. The resulting powder was analyzed by ¹ H-NMR, whereby the formation of the target compound was confirmed.

[0108]

Example 21: Synthesis of 1,3-dihexylurea

Yellow crystals were obtained (yield by mass: 0.08 g, yield: 14%) as in Example 17 above, except that ethylamine hydrochloride (0.82 g, 10 mmol) was used instead of aniline, the reaction temperature was 10°C , the reaction time was 5 hours, and after the reaction, ethyl acetate was used instead of dichloromethane. The resulting crystals were analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0109]

Example 22: Synthesis of 1,3-dipiperidinylurea

Yellow crystals were obtained (yield by mass: 0.38 g, yield: 38%) as in Example 17 above, except that piperidine (0.85 g, 10 mmol) was used instead of aniline, the reaction time was 3 hours, and the title compound was purified using a short silica gel column (eluent: dichloromethane). The resulting crystals were analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0110]

Example 23: Photoinduced copolymerization of bisphenol A and hexamethylenediamine

The reaction was carried out at 20° C. for 2 hours in the same manner as in Example 8 above, except that diazabicycloundecene (60 mmol) was used instead of aqueous sodium hydroxide solution. The reaction was then further carried out at 50° C. for 15 minutes. After the reaction, water was added and the reaction mixture was left to stand overnight. Then the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was washed with hexane and dried at 70° C. under reduced pressure. After the residue was further washed with dichloromethane and hexane, the residue was dried under reduced pressure to give a light orange powder (yield: >99%). The resulting powder was analyzed by ¹ H-NMR and IR, as a result of which the formation of the target copolymer was confirmed.

[0111]

Example 24: Synthesis of 1,3-diphenylurea

Purified chloroform (20 ml), aniline (0.93 g, 10 mmol) and pyridine (4.01 ml, 50 mmol) were added to the reaction vessel described above, and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 2 hours, dichloromethane and water were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The residue thus obtained was dissolved in dichloromethane and ethyl acetate, and the aniline black was removed by passing the solution through an alumina column. The liquid purified by the column was concentrated under reduced pressure, and the residue was recrystallized using ethyl acetate and hexane to give light brown needles (yield by mass: 0.54 g, yield: 51%). The resulting crystals were analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0112]

Example 25: Synthesis of 1,3-diphenylurea

The reaction was carried out at 20° C. for 2 hours in the same manner as in Example 24 above, except that diazabicycloundecene (7.48 ml, 50 mmol) was used instead of pyridine. After the reaction, dichloromethane and water were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The residue thus obtained was dissolved in THF and the impurity was removed by passing the solution through an alumina column. The liquid purified by the column was concentrated under reduced pressure, and the residue was recrystallized using dichloromethane and hexane to give light orange crystals (yield by mass: 0.44 g, yield: 38%).

[0113]

Example 26: Synthesis of 1,3-dicyclohexylurea

The reaction was carried out at 20° C. for 4 hours in the same manner as in Example 24 above, except that cyclohexylamine (1.17 ml, 10 mmol) was used instead of aniline. After the reaction, dichloromethane and water were added, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was recrystallized using dichloromethane and hexane to give light brown crystals (yield by mass: 0.16 g, yield: 14%). The resulting crystals were analyzed by ¹ H-NMR, which confirmed the formation of the target compound.

[0114]

Example 27 Synthesis of Polyurea

Purified chloroform (20 mL), 4,4'-diaminodiphenyl ether (0.50 g, 2.5 mmol) and pyridine (1.0 mL, 12.5 mmol) were added to the reaction vessel described above and the mixture was stirred to mixing. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After 1.5 hours, dichloromethane and water were added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure. The residue thus obtained was washed with methanol to obtain a brown powder (yield by mass: 0.14 g, yield: 25%). The resulting crystals were analyzed by ¹ H-NMR and IR, which confirmed the formation of the target compound.

[0115]

Example 28: Synthesis of carbonyldiimidazole

Purified chloroform (20 ml), imidazole (0.68 g, 10 mmol) and 2,6-lutidine (5.79 ml, 50 mmol) were added to the reaction vessel described above and the mixture was stirred to mix. Gaseous oxygen was blown into the stirred reaction mixture at a flow rate of 0.5 L/min at 20° C. to induce bubbling, and irradiated with light from a low pressure mercury lamp. After the termination of irradiation, the reaction was carried out at 50°C for 30 min. Dichloromethane (5 ml) was added to the reaction mixture as an internal standard, and the reaction mixture was analyzed by ¹ H-NMR, whereby the formation of the title compound was confirmed in 38% yield.

[0116]

Example 29 Synthesis of S,S'-diphenyldithiocarbonate

Purified chloroform (20 ml), thiophenol (1.03 ml, 10 mmol) and aqueous sodium hydroxide solution (NaOH: 4 g, 20 mmol) were added to the above reaction vessel, and the mixture was stirred to mix. Oxygen gas was blown into the stirred reaction mixture at a flow rate of 0.5 L/min to induce bubbling, and irradiated with light from a low pressure mercury lamp to carry out the reaction at 20° C. for 2 hours. Dichloromethane and water were then added to the reaction mixture, and the organic phase and the aqueous phase were separated. The organic phase was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to give a brown liquid. The resulting brown liquid was analyzed by ¹ H-NMR, which confirmed the formation of the target compound in 20% yield.

DESCRIPTION OF REFERENCE NUMBERS

[0117]

1: light irradiation means,

2: shirt,

3: water bath,

4: stirring rod,

5: heat transfer medium or cooling medium,

6. tubular reaction vessel

Claims (22)

1. A method for producing a carbonate derivative, including irradiating with light a composition containing a halogenated methane having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a compound containing a nucleophilic functional group, and a base in the presence of oxygen, where the compound containing the nucleophilic functional group is represented by the following formula (i), and the carbonate derivative is a linear carbonate derivative represented by the following formula (I), or a compound containing a nucleophilic functional group represented by the following formula (ii), bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol TMC, and bisphenol Z, and the carbonate derivative is a polycarbonate derivative containing a moiety represented by the following formula (II-1 ), a polycarbonate ester of bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol TMC, or bisphenol Z, or a cyclic carbonate derivative represented by the following formula (II–2), and where the base is one or more bases selected from the group consisting of a heterocyclic aromatic amine, a non-nucleophilic strong base and an inorganic base, where the heterocyclic aromatic amine is pyridine or a pyridine derivative selected from the group consisting of α-picoline, β-picoline, γ-picoline, 2,3-lutidine, 2,4-lutidine, 2,6-lutidine, 3.5 -lutidine, 2-chloropyridine, 3-chloropyridine and 4-chloropyridine, where the non-nucleophilic strong base is 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8- diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,1,3,3-tetramethylguanidine, and where the inorganic base is an alkali metal hydroxide, an alkali metal carbonate or an alkali metal hydrogen carbonate, (i) R ¹ –A–H, (ii) H–A–R ² –A–H, (I) R ¹ –A–C(=O)–A–R ¹ , (II–1) [–A–R ² –A–C(=O)–],

, where A is O, S or NR ³ where R ³ is an H or C _1-4 alkyl group or R ³ forms a nitrogen heterocyclic group with R ¹ and N, R ¹ is a C _6-14 aryl group, a C _4-14 heteroaryl group, or a C _2-24 alkylpolyoxyalkylene group, R ² is a C _2-10 alkylene group, a C _6-14 arylene group, a C _4-14 heteroarylene group, or a C _2-24 polyoxyalkylene group. 2. The production method according to claim 1, wherein the halogenated methane is chloroform. 3. The production process according to any one of claims 1 to 2, wherein the heterocyclic aromatic amine is pyridine, picoline or lutidine. 4. The production method according to any one of claims 1 to 3, wherein 0.001 times or more and 1 times or less the molar amount of the compound containing the nucleophilic functional group relative to halogenated methane is used. 5. The production method according to any one of claims 1 to 4, in which 1.5 times or more and 10 times or less the molar amount of base relative to the compound containing the nucleophilic functional group is used. 6. The production method according to any one of claims 1 to 5, wherein the wavelength of the light irradiating the composition is 180 nm or more and 500 nm or less.

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