阅读说明：本技术 碳酸酯衍生物的制备方法 (Process for producing carbonate derivative ) 是由 津田明彦 于 2018-04-27 设计创作，主要内容包括：本发明的目的在于提供一种用于安全且有效地制备碳酸酯衍生物的方法。本发明涉及的碳酸酯衍生物的制备方法,其特征在于,对含有具有选自由氯原子、溴原子和碘原子组成的组中的1种以上的卤素原子的C<Sub>1-4</Sub>卤代烃、含亲核性官能团的化合物以及特定的碱的组合物,在氧存在下进行光照射。(The object of the present invention is to provide a method for safely and efficiently producing a carbonate derivative. The process for producing a carbonate derivative of the present invention is characterized in that the compound having a structure selected from the group consisting of a chlorine atom, a bromine atom and an iodine atomC of 1 or more halogen atoms in the group 1‑4 A composition comprising a halogenated hydrocarbon, a nucleophilic functional group-containing compound and a specific base is irradiated with light in the presence of oxygen.)

1. A method for producing a carbonate derivative, which is a method for producing a carbonate derivative, wherein,

for C containing 1 or more halogen atoms selected from the group consisting of chlorine atom, bromine atom and iodine atom_1-4A composition of a halogenated hydrocarbon, a compound having a nucleophilic functional group, and a base, irradiated with light in the presence of oxygen,

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

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

as the base, 1 or more bases selected from the group consisting essentially of heterocyclic aromatic amines, strong non-nucleophilic bases, and inorganic bases are used;

(i) R¹-A-H

(ii) H-A-R²-A-H

(I) R¹-A-C(＝O)-A-R¹

(II-1) [-A-R²-A-C(＝O)-]

[ chemical formula 1]

(II-2)

Wherein A is O, S or NR³(R³Is H or C_1-4Alkyl, or R¹And N may together form a nitrogen-containing heterocyclic group),

R¹is C_6-14Aryl radical, C_4-14Heteroaryl or C_2-24An alkyl polyoxyalkylene group, which is a polyoxyalkylene group,

R²is C_2-10Alkylene radical, C_6-14Arylene radical, C_4-14Heteroarylene or C_2-24A polyoxyalkylene group.

2. The method for preparing according to claim 1, wherein the C is_1-4The halogenated hydrocarbon being C_1-4A polyhalogenated hydrocarbon.

3. The method for preparing according to claim 1, wherein the C is_1-4The halogenated hydrocarbon is chloroform.

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

5. The process according to any one of claims 1 to 4, wherein the strong non-nucleophilic 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.

6. The production method according to any one of claims 1 to 5, wherein the inorganic base is an alkali metal hydroxide, an alkali metal hydrogencarbonate or an alkali metal carbonate.

7. The method for preparing a compound according to any one of claims 1 to 6, wherein C is used_1-4The amount of the halogenated hydrocarbon is 0.001 to 1 mol per mol of the nucleophilic functional group-containing compound.

8. The production method according to any one of claims 1 to 7, wherein the base is used in an amount of 1.5-fold mol or more and 10-fold mol or less relative to the nucleophilic functional group-containing compound.

9. The production method according to any one of claims 1 to 8, wherein the light irradiated to the composition has a wavelength of 180nm to 500 nm.

Technical Field

The present invention relates to a method for safely and efficiently producing a carbonate derivative.

Background

Conventionally, a chain carbonate in a carbonate derivative has been generally used as a solvent or the like, and particularly in recent years, the yield thereof has been increased as a nonaqueous solvent for an electrolyte of a lithium ion secondary battery. In addition, polycarbonate, which is a condensation product of carbonic acid and a bisphenol compound, is widely used as an engineering plastic having good transparency and impact resistance. In addition, urea resins are widely used as binders and materials for tableware. Polydithiocarbonates are expected to be used as stable optical materials with little coloration.

Carbonate derivatives are generally prepared from phosgene and compounds containing nucleophilic functional groups. However, phosgene is a very toxic substance, because phosgene easily reacts with water to generate hydrogen chloride, and has a history of use as a toxic gas. In addition, there is a method of reacting carbon monoxide, alcohol and oxygen, but there is a problem that toxic carbon monoxide must be used under high pressure. Thus, various studies have been made on safe processes for producing carbonates and polycarbonates.

For example, patent document 1 discloses a method for producing a desired carbonate derivative by subjecting a carbonate to a transesterification reaction in the presence of a catalyst. However, this method still has a problem of how to prepare a carbonate derivative as a starting compound, and is not a fundamental solution. In addition, there is a problem that an expensive catalyst must be used, and a reverse reaction and a side reaction are caused by a residual catalyst.

Patent document 2 discloses a method for producing a carbonate derivative from an epoxy compound and carbon dioxide in the presence of a catalyst. In this method, phosgene or carbon monoxide is not required, but an expensive catalyst must be used, and carbon dioxide must be increased in pressure, which is not suitable for industrial mass production.

The inventors of the present invention have developed a method for producing a halogenated carboxylic acid ester by a photoreaction of a halogenated hydrocarbon and an alcohol by oxidation (patent document 3), and a method for producing a halogenated carboxylic acid ester, which comprises a step of irradiating chloroform with light in the presence of oxygen to obtain a mixture containing phosgene, and a step of reacting an alcohol with the mixture without separating phosgene (patent document 4).

Disclosure of Invention

As described above, phosgene is generally used for the production of carbonate derivatives, and even in a production method in which phosgene is not used, there are problems in that other toxic compounds and expensive catalysts are used, or in that phosgene must be used for the production of raw material compounds.

Accordingly, an object of the present invention is to provide a method for safely and efficiently producing a carbonate derivative.

The present inventors have conducted intensive studies to solve the above problems. As a result, they have found that a carbonate derivative can be produced unexpectedly safely and efficiently by carrying out a photoreaction on a hydrocarbon compound substituted with a halogen group and a specific nucleophilic functional group-containing compound in the presence of oxygen and a specific base, thereby completing the present invention. In general, it is known that an organic base forms a dye by photoreaction, functions as an antioxidant for trapping radicals, quenches fluorescence of a compound by a mechanism such as electron transfer, or decomposes pyridine into glutaraldehyde or the like by ultraviolet rays (non-patent documents 1 to 3), and it is considered that the organic base is disadvantageous to photoreaction of the inventions of patent document 3 and patent document 4 developed by the present inventors. In contrast, the efficient formation of carbonate derivatives in the photoreaction in the presence of specific bases is very surprising.

The present invention is described below.

[1] A method for producing a carbonate derivative, which is a method for producing a carbonate derivative, wherein,

for C containing 1 or more halogen atoms selected from the group consisting of chlorine atom, bromine atom and iodine atom_1-4A composition of a halogenated hydrocarbon, a compound having a nucleophilic functional group, and a base, irradiated with light in the presence of oxygen,

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

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

as the base, 1 or more bases selected from the group consisting essentially of heterocyclic aromatic amines, strong non-nucleophilic bases, and inorganic bases are used.

(i) R¹-A-H

(ii) H-A-R²-A-H

(I) R¹-A-C(＝O)-A-R¹

(II-1) [-A-R²-A-C(＝O)-]

[ chemical formula 1]

[ in the formula,

a is O, S or NR³(R³Is H or C_1-4Alkyl, or R¹And N may together form a nitrogen-containing heterocyclic group),

R¹is C_6-14Aryl radical, C_4-14Heteroaryl or C_2-24An alkyl polyoxyalkylene group, which is a polyoxyalkylene group,

R²is C_2-10Alkylene radical, C_6-14Arylene radical, C_4-14Heteroarylene or C_2-24A polyoxyalkylene group.]

[2]According to the above [1]The production process of (A), wherein C_1-4The halogenated hydrocarbon being C_1-4A polyhalogenated hydrocarbon.

[3]According to the above [1]The production process of (A), wherein C_1-4The halogenated hydrocarbon is chloroform.

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

[5] The production process according to any one of the above [1] to [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.

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

[7]According to the above [1]-[6]The production method of any one of the above, wherein C is used_1-4The amount of the halogenated hydrocarbon is 0.001 to 1 mol per mol of the nucleophilic functional group-containing compound.

[8] The production method according to any one of the above [1] to [7], wherein the base is used in an amount of 1.5 to 10 moles based on the nucleophilic functional group-containing compound.

[9] The production method according to any one of the above [1] to [8], wherein the light to be irradiated to the composition has a wavelength of 180nm to 500 nm.

In the process of the present invention, it is not necessary to use highly toxic compounds such as phosgene or carbon monoxide, and it is not necessary to use expensive catalysts as the starting compounds. Therefore, the method of the present invention is industrially extremely useful as a technique capable of producing a useful carbonate derivative safely and efficiently.

Drawings

FIG. 1 is a schematic diagram showing an example of the structure of a reaction apparatus used in the method of the present invention.

Detailed Description

In the method for producing a carbonate derivative according to the present invention, a compound having at least 1 halogen atom selected from the group consisting of chlorine atom, bromine atom and iodine atom is reacted with C_1-4A composition comprising a halogenated hydrocarbon, a nucleophilic functional group-containing compound and a specific base is irradiated with light in the presence of oxygen.

1.C_1-4Halogenated hydrocarbons

In the reaction according to the invention, C_1-4It is considered that the halogenated hydrocarbon is decomposed by irradiation light and oxygen to be converted into a carbonyl halide or a carbonyl halide compound, and reacts with the hydroxyl group-containing compound to produce a carbonate derivative. Even if a harmful carbonyl halide is produced, the carbonyl halide reacts with the hydroxyl group-containing compound immediately because of its extremely high reactivity, and does not leak out of the reaction solution or leaks out to a very small extent. In addition, phosgene as a carbonyl halide, for example, is very toxic and is subject to severe restrictions in its transport and the like, C_1-4Halogenated hydrocarbons are certainly not so dangerous. However, as described later, the reaction according to the present invention may be carried out in the presence of an aqueous inorganic base solution, and therefore, a carbonyl halide or a compound such as a carbonyl halide may not be involved in the reaction according to the present invention.

In particular C which is liquid at normal temperature and pressure_1-4Halogenated hydrocarbons are largely eliminated as organic solvents and the likeOn the other hand, emission into the atmosphere causes environmental pollution such as air pollution and ozone layer destruction. The invention is to decompose the C by light_1-4The art of preparing useful compounds from halogenated hydrocarbons has contributed greatly in industry and environmental science.

C_1-4The halogenated hydrocarbon is an alkane, alkene or alkyne having 1 to 4 carbon atoms, which is substituted with 1 or more halogen atoms selected from the group consisting of chlorine atoms, bromine atoms and iodine atoms. As described above, in the present invention C_1-4The halogenated hydrocarbon is decomposed by irradiation with light and oxygen, and is considered to function similarly to a carbonyl halide. Therefore, it is preferably C_1-2The halogenated hydrocarbon compound is more preferably a halogenated methane. When the number of carbon atoms is 2 to 4, it is preferably an alkene or alkyne having 1 or more unsaturated bonds in order to facilitate decomposition. Further, C having 2 or more of the above halogen atoms is preferable_1-4A halogenated hydrocarbon. Further, it is preferable that C having 2 or more halogen atoms on the same carbon is converted with decomposition of the halogen atom_1-4A polyhalogenated hydrocarbon compound.

As a particular C_1-4Halogenated hydrocarbons, preferably C_1-4Halogenated alkanes, C_2-4Halogenated olefins or C_2-4The halogenated alkyne is more preferably a methyl halide, a vinyl halide or a halogenated acetylene, particularly preferably a polyhalomethane, a polyhaloethylene or a polyhaloacetylene having 2 or more halogen atoms as described above, and most preferably a polyhalomethane, from the viewpoint of easily generating a compound such as a carbonyl halide. As C_1-4Examples of the halogenated hydrocarbon include halogenated methanes such as dichloromethane, chloroform, dibromomethane, bromoform, iodomethane, and diiodomethane; halogenated ethanes 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; perhaloalkanes such as tetrachloromethane, tetrabromomethane, tetraiodomethane, hexachloroethane, and hexabromoethane; perhaloethylenes such as 11,2, 2-tetrachloroethylene and 1,1,2, 2-tetrabromoethylene.

C_1-4Halogenated hydrocarbons may be targetedThe chemical reaction and the desired product are appropriately selected, and 1 kind may be used alone, or 2 or more kinds may be used in combination. Preferably, only 1C is used, depending on the preparation of the target compound_1-4A halogenated hydrocarbon. C_1-4Among the halogenated hydrocarbons, compounds having a chlorine group are preferable.

C used in the method of the present invention_1-4The halogenated hydrocarbon may be, for example, C recovered and used as a solvent_1-4A halogenated hydrocarbon material. In this case, since a large amount of impurities and water may inhibit the reaction, it is preferable to perform purification to some extent. For example, it is preferable to remove water and water-soluble impurities by washing with water and then dehydrate with anhydrous sodium sulfate, anhydrous magnesium sulfate, or the like. However, it is considered that the reaction proceeds even when water is contained, and therefore, excessive purification which deteriorates the productivity is not necessary. The water content is more preferably 0.5% by volume or less, still more preferably 0.2% by volume or less, and still more preferably 0.1% by volume or less. Further, the above-mentioned reuse C_1-4In the halogenated hydrocarbon, may contain C_1-4Decomposition products of halogenated hydrocarbons, and the like.

2. Compounds containing nucleophilic functional groups

In the present invention, the "nucleophilic functional group-containing compound" refers to a compound including a nucleophilic functional group containing a nucleophilic oxygen atom, a sulfur atom and/or a nitrogen atom, and is a compound represented by formula (i) or formula (ii), and the compound represented by formula (i) or formula (ii) is also simply referred to as "nucleophilic functional group-containing compound (i)" or "nucleophilic functional group-containing compound (ii)" respectively. The nucleophilic functional group-containing compound used in the present invention has no fluorine atom as a substituent. As a result, the carbonate derivative produced by the process of the present invention does not have a fluorine atom as a substituent. In the present invention, the reaction can be carried out to a carbonate derivative by using a specific nucleophilic functional group-containing compound.

In the present invention, when the nucleophilic functional group-containing compound (I) is used, the obtained carbonate derivative is a chain carbonate represented by the formula (I) (hereinafter also referred to simply as "chain carbonate (I)"), and when the hydroxyl group-containing compound (II) is used, the obtained carbonate derivative is a polycarbonate derivative comprising a unit represented by the formula (II-1) (hereinafter also referred to simply as "polycarbonate derivative (II-1)") or a cyclic carbonate derivative represented by the formula (II-2) (hereinafter also referred to simply as "cyclic carbonate derivative (II-2)").

In the production method of the present invention, the nucleophilic functional group-containing compound (I) and the nucleophilic functional group-containing compound (II) used as the raw material compounds, and the chain carbonate derivative (I), the polycarbonate derivative (II-1), and the cyclic carbonate derivative (II-2) as the target compounds are as follows.

(i) R¹-A-H

(ii) H-A-R²-A-H

(I) R¹-A-C(＝O)-A-R¹

(II-1) [-A-R²-A-C(＝O)-]

[ chemical formula 2]

[ in the formula,

a is O, S or NR³(R³Is H or C_1-4Alkyl, or R¹And N may together form a nitrogen-containing heterocyclic group),

R¹is C_6-14Aryl radical, C_4-14Heteroaryl or C_2-24An alkyl polyoxyalkylene group, which is a polyoxyalkylene group,

R²is C_2-10Alkylene radical, C_6-14Arylene radical, C_4-14Heteroarylene or C_2-24A polyoxyalkylene group.]

In the present specification, a halogenated hydrocarbon having 1 to 4 carbon atoms is represented by "C_1-4A halogenated hydrocarbon ". Other groups and other compounds are also described in the same manner.

As R in the nucleophilic functional group-containing compound (i)³Preferably, H is used. In addition, R¹、R³The nitrogen-containing heterocyclic group formed by N may be a non-aromatic nitrogen-containing heterocyclic group or an aromatic nitrogen-containing heterocyclic group. AsExamples of the non-aromatic nitrogen-containing heterocyclic group include a pyrrolidinyl group and a piperidinyl group. Examples of the aromatic nitrogen-containing heterocyclic group include a pyrrolyl group, an imidazolyl group and a pyrazolyl group.

C_6-14The hydrogen atom of the aryl group may be substituted by a chlorine atom, a bromine atom, an iodine atom or C_1-8Alkyl substitution.

C_4-14The heteroaryl group means an aromatic heterocyclic group having 1 or more nitrogen atoms, oxygen atoms or sulfur atoms. Examples of the heterocyclic group include 5-membered ring heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazolyl; 6-membered ring heteroaryl such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like; a condensed aromatic heterocyclic group such as indolyl, isoindolyl, quinolyl, isoquinolyl, benzofuranyl, isobenzofuranyl, chromenyl and the like, preferably C containing a nitrogen atom_4-14Heteroaryl, more preferably pyridyl.

As C_2-24Alkylpolyoxyalkylene, preferably of the formula- (Q)^HO)_mR^HA group represented by the formula (I). However, Q^His-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH(CH₃) -or-CH₂CH₂CH₂CH₂-，R^His-CH₃or-CH₂CH₃And m is an integer of 1 to 20 inclusive. When M is 2 or more, Q^HThe composition may be composed of only 1 kind or may be composed of a plurality of kinds. Q^HWhen the composition is composed of a plurality of kinds, Q is a plurality of kinds^HThe arrangement of (A) may be random or block.

As C_2-24Polyoxyalkylene, preferably of the formula- (Q)^HO)_mQ^H-a group represented by the group.

C_2-10The alkylene group may be linear, branched or cyclic. As C_2-10Alkylene, preferably C_2-6Alkylene, more preferably C_2-4An alkylene group. In addition, from the viewpoint of easy availability of the cyclic carbonate, it is preferableIs optionally 1 or 2C_1-4Alkyl-substituted vinyl, more preferably C optionally substituted by 1 or 2_1-2Alkyl-substituted vinyl, more preferably vinyl optionally substituted with 1 or 2 methyl groups. Furthermore, vinyl groups optionally substituted with the above-mentioned alkyl groups may also be described as 1, 2-alkylene groups.

C_6-14Arylene radical, C_4-14Heteroarylene and C_2-24Polyoxyalkylene radicals, each being a radical corresponding to C_6-14Aryl radical, C_4-14Heteroaryl and C_2-24An alkyl polyoxyalkylene 2-valent organic group.

Examples of the nucleophilic functional group-containing compound (i) include a hydroxyl group-containing compound (i), a thiol group-containing compound (i), and an amino group-containing compound (i). Examples of the hydroxyl group-containing compound (i) include phenols such as phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-methylphenol, 3-methylphenol, and 4-methylphenol, and derivatives thereof; c of cyclohexanol or the like_3-10A cycloalkanol; benzyl alcohol and derivatives thereof such as benzyl alcohol and 2, 6-benzyl alcohol; alkylene glycol mono C such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether_1-4An alkyl ether; oligo-alkylene glycol mono-C such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and tetraethylene glycol monomethyl ether_1-4An alkyl ether.

Examples of the thiol group-containing compound (i) include thiophenols such as thiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 2-methylthiophenol, 3-methylthiophenol, and 4-methylthiophenol, and derivatives thereof; c of cyclohexanethiol or the like_3-10A cycloalkanethiol; benzyl mercaptan such as benzyl mercaptan, 2-chlorobenzyl mercaptan, 4-chlorobenzyl mercaptan, and 4-methoxybenzyl mercaptan, and derivatives thereof; HSCH₂CH₂SCH₃、HSCH₂CH(CH₃)SCH₃、HSCH(CH₃)CH₂SCH₃Iso-1, 2-ethanedithiol-mono-C_1-4An alkyl thioether; oligo (1, 2-ethanedithiol) alkylene glycol mono C such as bis (1, 2-ethanedithiol) monomethyl sulfide, tris (1, 2-ethanedithiol) monomethyl sulfide, tetrakis (1, 2-ethanedithiol) monomethyl sulfide_1-4An alkyl thioether.

Examples of the amino group-containing compound (i) include anilines such as aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-methylaniline, 3-methylaniline and 4-methylaniline, and derivatives thereof; c of cyclohexylamine or the like_3-10A cycloalkylamine; heterocyclic amines such as piperazine or piperidine; benzyl alcohols and derivatives thereof such as benzylamine, 4- (aminomethyl) benzonitrile, 2-chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-bromobenzylamine, 3-bromobenzylamine, 4-bromobenzylamine, and 4-tert-butylbenzylamine; alkylene glycol mono C such as N-methylethylenediamine, N-dimethylethylenediamine, N-methylpropylenediamine, and N, N-dimethylpropylenediamine_1-4An alkyl ether; n-monoc such as N-methyldiethylenetriamine, N-dimethyldiethylenetriamine, N-methyltriethylenetetramine, N-dimethyltriethylenetetramine, N-methyltetraethylenepentamine, and N, N-dimethyltetraethylenepentamine_1-4Alkyl oligo-or N, N-di-C_1-4An alkyl oligo-ethylene diamine.

The nucleophilic functional group-containing compound (i) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. For example, by using 2 kinds of nucleophilic functional group-containing compounds (i) in combination, a non-target chain carbonate derivative can be synthesized. However, from the viewpoint of production efficiency and the like, it is preferable to use only 1 species of the nucleophilic functional group-containing compound (i) alone.

As the nucleophilic functional group-containing compound (ii), compounds represented by the following formulae (ii-1) and (ii-2) are preferable.

(ii-1) H-A-R²¹-A-H

(ii-2) H-A-R²²-R²³-R²⁴-A-H

[ in the formula,

a is a group having the same meaning as above,

R²¹is C_2-10Alkylene radical, C_6-14Arylene radicals or C_4-14A hetero-arylene group,

R²²and R²⁴Each independently is C_6-14Arylene radicals or C_4-14A hetero-arylene group,

R²³is C1-10 alkyleneAnd (4) a base.]

When the hydroxyl group-containing compound (II) is used as a starting material compound, a polycarbonate derivative (II-1) or a cyclic carbonate derivative (II-2) is obtained. Specifically, R²When the number of carbon atoms of the main chain contained in (a) is 2 or 3, and a stable structure such that a carbonate group (-O-C (═ O) -O-), a carbonic acid dithioester group (-S-C (═ O) -S-) or a carbonic acid amide group (-NH-C (═ O) -NH-) forms a five-membered ring or a six-membered ring together, a cyclic carbonate derivative is mainly produced. In particular, C in the nucleophilic functional group-containing compound (ii-1)_2-10Alkylene radical, C_6-14Arylene and C_4-14Heteroarylene radicals being each 1,2-C_2-10Alkylene, 1,2-C_6-14Arylene and 1,2-C_4-14In the case of heteroarylene, a cyclic carbonate is mainly produced. R²When the number of carbon atoms in the main chain contained in (2) is 4 or more, a chemically more stable one is preferentially formed between the cyclic carbonate derivative and the polycarbonate derivative, depending on the reaction conditions and the like.

In addition, in the 1, 2-arylene group, in addition to the 1, 2-phenylene group and the 1, 2-biphenylene group, the structure is included in 1, 2-naphthylene, 1, 8-naphthylene, and 2, 3-naphthylene having the following structures. 1,2-C_2-10Alkylene and 1,2-C_4-14The same applies to heteroarylene.

[ chemical formula 3]

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

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

[ chemical formula 4]

Examples of the thiol group-containing compound (ii) include C such as 1, 2-propanedithiol, 1, 2-ethanedithiol and 1, 4-butanedithiol_1-4An alkylene dithiol compound; benzenedithiol compounds such as 1, 2-benzenedithiol and 1, 3-benzenedithiol; heteroaryl dithiol compounds such as 2-methylpyrimidine-4, 6-dithiol and 4-methylpyridazine-3, 6-dithiol; bis-thiophenol compounds such as 4,4' -thiobis-benzenethiol, 2-bis (4-mercaptophenyl) propane, 1-bis (4-mercaptophenyl) -1-phenylethane, 2-bis (4-mercaptophenyl) butane, bis (4-mercaptophenyl) diphenylmethane, 1-bis (4-mercaptophenyl) ethane, bis (4-mercaptophenyl) methane, 1-bis (4-mercaptophenyl) -3,3, 5-trimethylcyclohexane and 1, 1-bis (4-mercaptophenyl) cyclohexane.

Examples of the amino group-containing compound (ii) include C's such as 1, 2-propanediamine, 1, 3-propanediamine, 1, 2-ethanediamine and 1, 4-butanediamine_1-4An alkylene diamine compound; phenylenediamine compounds such as 1, 2-phenylenediamine and 1, 4-phenylenediamine; heteroaryl dithiol compounds such as 4, 6-diamino-2-methylpyrimidine and 3, 6-diamino-4-methylpyridazine; diaminobenzene compounds such as 2, 2-bis (4-aminophenyl) propane, 1-bis (4-aminophenyl) -1-phenylethane, 2-bis (4-aminophenyl) butane, bis (4-aminophenyl) diphenylmethane, 1-bis (4-aminophenyl) ethane, bis (4-aminophenyl) methane, 1-bis (4-aminophenyl) -3,3, 5-trimethylcyclohexane and 1, 1-bis (4-aminophenyl) cyclohexane.

C_1-4The amount of the halogenated hydrocarbon and the nucleophilic functional group-containing compound used is not particularly limited as long as the reaction proceeds to obtain the desired product, and is, for example, relative to C_1-4The above reaction also proceeds when 1-fold mol of the nucleophilic functional group-containing compound is used for the number of moles of the halogenated hydrocarbon. In addition, from the reaction efficiencyFrom the viewpoints of rate, reaction time, etc., relative to C_1-4Molar ratio of nucleophilic functional group-containing compound of halogenated hydrocarbon ([ nucleophilic functional group-containing compound ]]/[C_1-4Halogenated hydrocarbons]) Preferably 0.001 to 1. The above molar ratio is more preferably 0.01 or more, still more preferably 0.1 or more, and still more preferably 0.8 or less, still more preferably 0.5 or less. When the molar ratio is too large, the amount of the nucleophilic functional group-containing compound increases relatively, and thus the amount of unreacted nucleophilic functional group-containing compound increases, whereas when the molar ratio is too small, unreacted C increases_1-4The halogenated hydrocarbon increases and the carbonyl halide may be released to the outside of the reaction system. In addition, C_1-4When the halogenated hydrocarbon is liquid at normal temperature and pressure and can be used as a solvent, it is used in comparison with C_1-4The proportion of the nucleophilic functional group-containing compound in the halogenated hydrocarbon may be 1mg/mL to 500 mg/mL.

3. Alkali

In the method of the present invention, 1 or more bases selected from the group consisting essentially of heterocyclic aromatic amines, strong non-nucleophilic bases and inorganic bases are used. By this base, the reaction proceeds until a polycarbonate derivative is produced.

Heterocyclic aromatic amines refer to compounds containing at least one heterocycle and having at least one amine functional group. Examples of the heterocyclic aromatic amine include pyridine and derivatives thereof such as 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.

The term "strong non-nucleophilic base" means that the nucleophilic property of a lone electron pair on a nitrogen atom due to steric hindrance is weak, and the basicity (pK) in acetonitrile is low_BH+) Is a base of 20 or more. Examples of the non-nucleophilic strong base include 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)。

Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate, and the like.

The inorganic base may be micronized before use and then added to the reaction solution as it is, and preferably an aqueous solution thereof. The concentration of the aqueous inorganic base solution may be adjusted as appropriate, and may be, for example, 0.05g/mL or more and 2g/mL or less. In addition, an aqueous solution of an inorganic base is used for the decomposition of phosgene. In particular, phosgene is decomposed in the presence of water into carbon dioxide and hydrogen chloride, which can be neutralized by an inorganic base. Therefore, the inventors of the present invention considered that the reaction according to the present invention proceeds via phosgene, and the reaction according to the present invention proceeds even in the case of using an aqueous solution of an inorganic base as in the examples described later, which is surprising. In addition, since the reaction according to the present invention proceeds even with an aqueous inorganic alkali solution, it may proceed without phosgene.

The alkali can be used alone only 1 kind, also can be more than 2 kinds of combination use.

The amount of the base used may be appropriately adjusted within a range in which the reaction proceeds well, and may be, for example, 1.5 to 10 mol based on the nucleophilic functional group-containing compound. In general, the yield is higher as the amount of the base used is larger, and the ratio is preferably 2.0 times by mole or more, more preferably 3.0 times by mole or more, and still more preferably 4.0 times by mole or more.

4. Reaction conditions

The method of the present invention includes the step of adding C_1-4A composition comprising a halogenated hydrocarbon, a nucleophilic functional group-containing compound and a base is subjected to a light irradiation step in the presence of oxygen.

C above_1-4The mixing method of the halogenated hydrocarbon, the nucleophilic functional group-containing compound, and the base is not particularly limited. For example, reactionIn the vessel, all the respective compounds may be premixed, may be added in several portions, or may be continuously added at an arbitrary rate. In addition, the above-mentioned C_1-4When one or both of the halogenated hydrocarbon and the nucleophilic functional group-containing compound are not liquid at normal temperature and pressure, a solvent which can appropriately dissolve these raw material compounds and does not inhibit the reaction of the present invention can be used. Examples of the solvent include aliphatic hydrocarbon solvents such as n-hexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; nitrile solvents such as acetonitrile.

The oxygen source may be any gas containing oxygen, and for example, air or purified oxygen may be used. The purified oxygen may be used in admixture with an inert gas such as nitrogen or argon. From the viewpoint of cost and easiness, air is preferably used. From increasing C induced by light irradiation_1-4From the viewpoint of the decomposition efficiency of the halogenated hydrocarbon, the oxygen content in the gas used as the oxygen source is preferably about 15 vol% or more and 100 vol% or less. The oxygen content may be in accordance with C_1-4The kind of the halogenated hydrocarbon and the like is appropriately determined. For example, as C above_1-4The halogenated hydrocarbon may be C of dichloromethane, chloroform, tetrachloroethylene, etc_1-4In the case of the chlorinated hydrocarbon compound, it is preferable to use C having an oxygen content of 15 vol% or more and 100 vol% or less, such as dibromomethane and bromoform_1-4In the case of the brominated hydrocarbon compound, the oxygen content is preferably 90 vol% or more and 100 vol% or less. Further, even in the case of using oxygen (oxygen content 100 vol%), the oxygen content can be controlled within the above range by adjusting the oxygen flow rate in the reaction system. The method for supplying the oxygen-containing gas is not particularly limited, and the oxygen-containing gas may be supplied into the reaction system from an oxygen cylinder equipped with a flow regulator, or may be supplied into the reaction system from an oxygen generator.

The term "in the presence of oxygen" means any of a state in which each of the above-mentioned compounds is in contact with oxygen and a state in which oxygen is present in the above-mentioned composition. Therefore, the reaction according to the present invention can be carried out under a gas flow of an oxygen-containing gas, and it is preferable that the oxygen-containing gas is supplied to the composition by bubbling from the viewpoint of improving the yield of the product.

Amount of oxygen-containing gas according to C_1-4The amount of the halogenated hydrocarbon, the shape of the reaction vessel, and the like may be determined as appropriate. For example, with respect to C as defined above present in the reaction vessel_1-4The amount of the halogenated hydrocarbon to be supplied to the reaction vessel per 1 minute is preferably 5 times or more by volume. This ratio is more preferably 25 times or more the capacity, and still more preferably 50 times or more the capacity. The upper limit of the ratio is not particularly limited, but is preferably 500 times or less by volume, more preferably 250 times or less by volume, and still more preferably 150 times or less by volume. In addition, with respect to the above-mentioned C present in the reaction vessel_1-4The amount of the hydrocarbon compound as oxygen supplied to the reaction vessel per 1 minute may be 5 to 25 times the capacity. When the flow rate of the gas is excessive, C is_1-4The hydrocarbon compound may be volatilized, and on the other hand, the reaction may be difficult to proceed when it is too small.

The light to be irradiated to the composition is preferably light including short-wavelength light, more preferably light including ultraviolet light, and still more preferably light including light having a wavelength of 180nm to 500 nm. Further, the wavelength of light is in accordance with C_1-4The kind of the halogenated hydrocarbon may be appropriately determined, and is more preferably 400nm or less, and still more preferably 300nm or less. When the irradiation light includes light in the wavelength range, C may be added_1-4Halogenated hydrocarbons are efficiently oxidatively decomposed.

The light irradiation means is not particularly limited as long as it can irradiate light of the above-mentioned wavelength, and examples of the light source including light of such a wavelength range in the wavelength region include sunlight, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light, a metal halide lamp, and an LED lamp. From the viewpoint of reaction efficiency and cost, a low-pressure mercury lamp is preferably used.

The conditions such as the intensity of the irradiation light and the irradiation time can be appropriately set according to the kind and the amount of the starting material, and for example, the intensity of the light is preferably 10. mu.W/cm²Above 500 muW/cm²The following. The light intensity is more preferably 100. mu.W/cm²Hereinafter, more preferably 40. mu.W/cm²The following. The irradiation time of light is preferably 0.5 hours to 10 hours, more preferably 1 hour to 6 hours, and still more preferably 2 hours to 4 hours. The light irradiation method is not particularly limited, and any one of a method of continuously irradiating light from the start of the reaction to the end thereof, a method of alternately repeating light irradiation and light non-irradiation, a method of irradiating light only for a predetermined time from the start of the reaction, and the like may be employed, and a method of continuously irradiating light from the start of the reaction to the end thereof is preferable.

The temperature during the reaction is not particularly limited, and may be appropriately adjusted, and may be, for example, 0 ℃ to 50 ℃. The temperature is more preferably 10 ℃ or higher, still more preferably 20 ℃ or higher, still more preferably 40 ℃ or lower, and still more preferably 30 ℃ or lower.

The reaction apparatus that can be used in the production method of the present invention includes a reaction apparatus having a light irradiation means on a reaction vessel. The reaction apparatus may be provided with a stirring device and a temperature control member. FIG. 1 shows one embodiment of a reaction apparatus which can be used in the production method of the present invention. The reaction apparatus shown in FIG. 1 is a reaction apparatus having a light irradiation means 1 in a cylindrical reaction vessel 6. The raw material compounds are added to the cylindrical reaction vessel 6, and the reaction is carried out by irradiating light with the light irradiation means 1 while supplying a gas containing oxygen to the reaction vessel 6 or bubbling a gas containing oxygen (not shown) in the composition. When the light irradiation means 1 is covered with a jacket 2 or the like, the jacket is preferably made of a material that transmits the short-wavelength light. In addition, the reaction vessel may be irradiated with light from the outside, and in this case, the reaction vessel is preferably made of a material which transmits the short-wavelength light. The material through which the short-wavelength light is transmitted is not particularly limited as long as the effect of the present invention is not impaired, and preferable examples thereof include quartz glass.

The product obtained by the above reaction can be purified by a conventionally known method. Examples of purification methods include distillation, evaporation under reduced pressure of the starting material compound, column chromatography, liquid separation, extraction, washing, and recrystallization.

When a hydroxyl group-containing compound, a thiol group-containing compound, or an amino group-containing compound is used as the nucleophilic functional group-containing compound of the raw material compound, carbonate derivatives having a carbonate group (-O — C (═ O) -O-), a carbonic acid dithioester group (-S-C (═ O) -S-), or a urea group (-NH-C (═ O) -NH-) are produced, respectively. When a hydroxyl group-containing compound and an amino group-containing compound are used in combination, a carbonate derivative having a carbamate group (-O — C (═ O) -NH-) is produced, and when a thiol group-containing compound and an amino group-containing compound are used in combination, a carbonate derivative having a thiocarbamate group (-S-C (═ O) -NH-) is produced.

The chain carbonate derivative (I) produced by the method of the present invention is useful as a nonaqueous solvent or the like, and for example, the chain carbonate (I) can be used as a solvent or the like for an electrolyte of a lithium ion secondary battery. Further, the polycarbonate (II) is useful as an excellent engineering plastic.

The present application claims the benefit of priority based on japanese patent application No. 2017-97681, filed on 5, 16, 2017. The entire contents of the specification of Japanese patent application No. 2017-97681, filed on 5/16/2017, are incorporated herein by reference.