JP2011207824A - Method for producing benzodioxane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply and efficiently producing a benzodioxane compound.SOLUTION: The target benzodioxane compound is obtained by reacting a phenol compound with a carbonate compound in the presence of a base. This method can produce the target substance industrially, simply and efficiently with high selectivity. If the benzodioxane compound obtained is reacted with a Lewis acid, a catechol compound that is a starting material for electrolyte salts for lithium secondary batteries, starting material for anion receptors for lithium secondary batteries and the like can be obtained simply and efficiently.

Description

  The present invention relates to a method for producing a benzodioxane compound.

  Benzodioxane compounds are known as additives (redox shuttle additives) for improving overcharge resistance in nonaqueous electrolyte batteries, particularly lithium secondary batteries (Patent Documents 1 and 2).

  A method for easily and efficiently producing this benzodioxane compound is desired.

  As a method for producing this benzodioxane compound, for example, in Non-Patent Document 1, perfluorobenzene is reacted with ethylene glycol and sodium hydroxide to obtain 2- (pentafluorophenoxy) ethanol, and N, N -A method of producing by reacting with potassium carbonate in dimethylformamide has been reported.

  However, in this method, a dimer is generated as a by-product in the first-stage reaction, so that the yield of the obtained benzodioxane compound is not good.

  Further, the production method is a two-stage reaction as described above, and after the first-stage reaction, a water washing treatment for removing NaF produced together with 2- (pentafluorophenoxy) ethanol is necessary. Furthermore, since the 2- (pentafluorophenoxy) ethanol is water-soluble, it must be extracted with an organic solvent. Therefore, there is a drawback that the manufacturing process becomes complicated.

  In Non-Patent Document 2, perfluorophenol and 2-bromoethanol are reacted to obtain 2- (pentafluorophenoxy) ethanol, which is further reacted with potassium carbonate in N, N-dimethylformamide. A method for producing a dioxane compound has been reported.

However, this method is also a two-stage reaction, and after the first-stage reaction, a water washing treatment for removing KF is necessary. It is also necessary to extract the 2- (pentafluorophenoxy) ethanol with an organic solvent. Therefore, there is a drawback that the manufacturing process becomes complicated. In addition, the above-described method uses a high-cost halogenated alcohol called BrCH ₂ CH ₂ OH, and thus has a problem of high production cost.

  Non-Patent Document 2 also reports a method of producing a benzodioxane compound by reacting perfluorophenol and ethylene oxide.

  However, ethylene oxide is explosive and difficult to handle and difficult to use on an industrial scale. Moreover, this method is also a two-stage reaction, in which potassium pentafluorophenolate is synthesized in the first stage and then reacted with ethylene oxide in the second stage. In the production method described above, it is necessary to continue to add the potassium pentafluorophenolate and ethylene oxide alternately so that a polymer of ethylene oxide as a by-product is not produced. Therefore, there is a drawback that the manufacturing process is complicated.

Moreover, the said benzodioxane compound can be converted into a catechol compound by removing the ethylene glycol part of the said benzodioxane compound. The catechol compound includes, for example, lithium bis [tetrafluoro-1,2-benzenediolato (2-)-O, O ′] borate useful as an electrolyte salt for a lithium secondary battery, an anion receptor for a lithium secondary battery. 2- (2,4-Difluorophenyl) -4-fluoro-1,3,2-benzodioxaborole, 2- (4-fluorophenyl) -tetrafluoro-1,3,2-benzodio, useful as Used as a raw material for xabolol, etc. As a method for producing this catechol compound, for example, Non-Patent Document 4 discloses that 2,2,3,3-tetrahydro-5,6,7,8-tetrafluoro-1,4-benzodioxane is added to AlCl ₃ in benzene. A method for producing it by reacting with it has been reported.

JP 2003-308874 A WO2008 / 140271 A1

Journal of Fluorine Chemistry 124 183-188 (2003) J. et al. Electrochem. Soc. , Vol. 143, no. 11, November 1996, 3572-3575. Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004) J. et al. Chem. Soc. 763 (1964)

  An object of this invention is to provide the method of manufacturing a benzodioxane compound simply and efficiently. Furthermore, it aims at providing the method of manufacturing a catechol compound simply and efficiently from a benzodioxane compound.

  As a result of intensive studies to solve the above problems, the present inventor can produce a benzodioxane compound with high purity and high yield by reacting a phenol compound with a carbonate compound that is easy to handle. I found. As a result of further research based on this knowledge, the present invention has been completed.

That is, this invention provides the manufacturing method of the following benzodioxane compounds.
1. General formula (3):

(In formula, R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are the same or different, respectively, and show a hydrogen atom, a fluorine atom, an alkyl group, or a fluorine-containing alkyl group.
In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group. )
A benzodioxane compound represented by the general formula (1):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
In the presence of a base, the phenol compound represented by general formula (2):

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as above).
The manufacturing method characterized by making it react with the carbonate compound represented by these.
2. The manufacturing method according to Item 1, wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom, a fluorine atom or a fluorine-containing alkyl group having 1 to 6 carbon atoms.
3. The manufacturing method according to Item 1 or 2, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each is a hydrogen atom or an alkyl group.
4). Item 4. The production method according to any one of Items 1 to 3, wherein the reaction is carried out in a polar solvent.
5. General formula (4):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group.)
A method for producing a catechol compound represented by:
(I) General formula (1):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
In the presence of a base, the phenol compound represented by general formula (2):

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group.)
Is reacted with a carbonate compound represented by the general formula (3):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as above.)
And (II) reacting the benzodioxane compound with a Lewis acid to produce a benzodioxane compound represented by general formula (4):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
A process for producing a catechol compound represented by:
The manufacturing method characterized by including.
6). Item 6. The method according to Item 5, wherein in the step (II), the reaction is performed with an aromatic hydrocarbon solvent.

  Hereinafter, the present invention will be described in more detail.

  The manufacturing method of the benzodioxane compound shown by General formula (3) and the catechol compound shown by General formula (4) described in this invention is shown below.

(In formula, R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are the same or different, respectively, and show a hydrogen atom, a fluorine atom, an alkyl group, or a fluorine-containing alkyl group.
In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group. )
The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is an alkyl group which may be linear or branched. Preferably it is a C1-C6, More preferably, it is a C1-C4 alkyl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like are exemplified, and a methyl group or an ethyl group is preferable.

The fluorine-containing alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is a group in which at least one hydrogen atom of a linear or branched alkyl group is substituted with a fluorine atom. Preferably it is a C1-C6, More preferably, it is a C1-C4 fluorine-containing alkyl group. Specifically, CH ₂ F—, CHF ₂ —, CF ₃ —, CF ₃ CF ₂ —, HCF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ —, (CF ₃ ) ₂ CH—, (CF ₃ ) ₂ CF-, CF ₃ CF ₂ CF ₂ CF _2- , (CF ₃ ) ₂ CF ₂ CF _2- , HCF ₂ CF ₂ CF ₂ CF _2-, etc. are exemplified, preferably CH ₂ F-, CHF _2- , CF ₃ —, CF ₃ CF ₂ — or HCF ₂ CF ₂ —.

R ¹ , R ² , R ³ and R ⁴ are each preferably a hydrogen atom, a fluorine atom or a fluorine-containing alkyl group having 1 to 6 carbon atoms. In particular, when R ¹ , R ² , R ³ and R ⁴ are all fluorine atoms, the voltage resistance is improved, which is most preferable from the viewpoint of being useful as a use application of the redox shuttle additive in a high voltage system. .

The alkyl group or fluorine-containing alkyl group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ is exemplified by the alkyl group or fluorine-containing alkyl group represented by R ¹ , R ² , R ³ and R ⁴ , respectively. And the same substituents can be exemplified.

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferred is at least one selected from the group consisting of a group or an ethyl group. When R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, it is most preferable from the viewpoint that the stability of the compound is increased.

  Hereinafter, the first step and the second step will be described in detail.

First Step First, the first step (step (I)) will be described. The first step includes a phenol compound represented by general formula (1) (hereinafter referred to as phenol compound (1)), a carbonate compound represented by general formula (2) (hereinafter referred to as carbonate compound (2)), and In the presence of a base to obtain a benzodioxane compound represented by the general formula (3) (hereinafter referred to as benzodioxane compound (3)).

  In the first step, the reaction is carried out in the presence of a base. Examples of the base used include inorganic bases.

  Examples of the inorganic base include alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; lithium hydroxide, sodium hydroxide and hydroxide Alkali metal hydroxides such as potassium; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; Preferably, it is an alkali metal carbonate.

  These bases can be used alone or in combination of two or more.

  The amount of the base used in the first step is usually about 0.1 to 5 mol, preferably 0.3 to 3 mol, relative to 1 mol of the phenol compound (1) as a substrate. Preferably it is 0.4-1.1 mol.

  The amount of the carbonate compound (2) used in the first step is usually about 1 to 10 mol, preferably 2 to 6 mol, more preferably 3 to 4 mol, per 1 mol of the phenol compound (1). preferable. By using the carbonate compound (2) within the above-mentioned range with respect to 1 mol of the phenol compound (1), the conversion of the reaction is sufficient and the target product can be obtained in a high yield. .

  In the first step, it is preferable to use a polar solvent as the reaction solvent. For example, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, tetrahydrofuran, glyme, diglyme, triglyme, tetraglyme, methyl ethyl ketone, acetone, methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, Water etc. can be illustrated and these mixed solvents may be used. In particular, at least one selected from the group consisting of dimethyl sulfoxide, N, N-dimethylformamide and N-methylpyrrolidone is preferable. In addition, these solvents can be used 1 type or in combination of 2 or more types.

  The concentration of the phenol compound (1) in the reaction solution in the first step is usually about 0.05 to 4 mol / L, preferably 0.5 to 1.5 mol / L, more preferably 1.2 to 1. 4 mol / L. That is, the amount of the reaction solvent may be appropriately set so as to be within the above-described concentration range. By setting the concentration of the phenol compound (1) in the reaction solution within the above range, the amount of the benzodioxan compound (3) obtained in one reaction increases (so-called scale merit occurs). Moreover, if the density | concentration of the phenol compound (1) in a reaction solution is in said range, since the amount of solvents is a small amount compared with a prior art, it becomes possible to improve the workability | operativity of a post-process.

  The reaction method in the first step is not particularly limited as long as the phenol compound (1) and the carbonate compound (2) are reacted. For example, a method of adding the phenol compound (1) to a reaction solvent in which a base and carbonate (2) are dissolved is exemplified. When adding the phenol compound (1), a pure substance of the phenol compound (1) may be added. However, in order to efficiently react the phenol compound (1) and the carbonate compound (2), a phenol compound ( After 1) is dissolved in a solvent, it is preferably added dropwise. In addition, it is preferable that the solvent which melt | dissolves a phenol compound (1) is the same as the reaction solvent which melt | dissolves the said base and carbonate compound (2).

  In the first step, the benzodioxane compound (3) is obtained by the reaction of the phenol compound (1) and the carbonate compound (2). In the above reaction, the general formula (5):

(In formula, R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are the same or different, respectively, and show a hydrogen atom, a fluorine atom, an alkyl group, or a fluorine-containing alkyl group.
In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group. )
Or a salt thereof (the salt is a salt formed between the compound represented by the general formula (5) and the above-mentioned base), and then the benzodioxane compound (3) is It is thought that it has been obtained. Therefore, the compound represented by the general formula (5) or a salt thereof can be isolated on the way as necessary.

The R ¹ , R ² , R ³ and R ⁴ in the compound represented by the general formula (5) or a salt thereof are each a hydrogen atom, a fluorine atom or a fluorine-containing alkyl group having 1 to 6 carbon atoms. Preferably, R ¹ , R ² , R ³ and R ⁴ are all fluorine atoms. The R ⁵ , R ⁶ , R ⁷ and R ⁸ in the compound represented by the general formula (5) or a salt thereof are each preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom or a carbon number 1-4 alkyl groups are more preferable, at least one selected from the group consisting of a hydrogen atom, a methyl group or an ethyl group is more preferable, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms. Most preferred.

  In the first step, the reaction temperature is usually about 130 to 175 ° C., whereby the phenol compound (1) and the carbonate compound (2) react to obtain the target benzodioxane compound (3). From the viewpoint of obtaining the benzodioxane compound (3) in a high yield without polymerizing the carbonate compound (2), the compound represented by the general formula (5) or a salt thereof is sufficient at about 100 to 130 ° C. A process having a stepwise temperature setting in which a cyclization reaction is performed at about 130 to 175 ° C. to obtain the benzodioxane compound (3) is preferable.

  The reaction time in the first step is not particularly limited. A part of the reaction solution is sampled as appropriate, and the reaction is confirmed after the disappearance of the compound represented by the phenol compound (1) and the general formula (5) or a salt thereof. Ends.

  Hereinafter, an example of a desirable mode of production of the benzodioxane compound (3) in the first step will be described in detail. A base such as potassium carbonate, a carbonate compound (2) such as ethylene carbonate, and a polar solvent such as dimethyl sulfoxide are mixed, and the starting phenol compound (1) is added. Furthermore, after stirring at the temperature of 100-130 degreeC, the compound shown by the said General formula (5) or its salt is fully produced | generated, it stirs at the temperature of 130-175 degreeC, and a ring-closing reaction is advanced. The disappearance of the phenol compound (1) and the compound represented by the general formula (5) or a salt thereof is confirmed, and the reaction is completed.

  The produced benzodioxane compound (3) can be isolated by a normal separation operation or extraction with an organic solvent such as ether. In addition, the benzodioxane compound (3) isolated as necessary can be further purified by distillation, sublimation or the like.

  In the method of the present invention, the benzodioxane compound (3) can be produced simply and efficiently. Moreover, the method of the present invention can produce the benzodioxane compound (3) with good yield.

Second Step Next, the second step (step (II)) will be described. The second step is a step of obtaining a catechol compound represented by the general formula (4) (hereinafter referred to as catechol compound (4)) by reacting the benzodioxane compound (3) with a Lewis acid.

Examples of the Lewis acid used in the second step include BF ₃ , BF ₃ .OEt ₂ , BBr ₃ , ZnCl ₂ , FeCl ₃ , AlCl ₃ , CoCl ₂ , NiCl ₂ , CuCl ₂ , TiCl ₄ , ZrCl ₄ , GeCl. ₄ , metal halides such as NbCl ₅ and their hydrates. Preferably, it is at least one selected from the group consisting of AlCl ₃ and BBr ₃ . These Lewis acids can be used alone or in combination of two or more.

  The amount of the Lewis acid used in the second step is usually about 2 to 10 mol, preferably 3 to 7 mol, and more preferably 4 to 6 mol with respect to 1 mol of the benzodioxane compound (3). By setting the amount of the Lewis acid within the above range, the conversion rate of the reaction is sufficient, and the target product can be obtained in a high yield.

  In the second step, an aromatic hydrocarbon solvent such as benzene, toluene, xylene and mesitylene can be used as a reaction solvent. Preferably, it is at least one selected from the group consisting of toluene and benzene, and more preferably toluene. In addition, these solvents can be used 1 type or in combination of 2 or more types.

  The concentration of the benzodioxane compound (3) in the reaction solution is usually about 0.1 to 2 mol / L, preferably 0.3 to 1.2 mol / L, more preferably 0.4 to 0.5 mol / L. . That is, the amount of the reaction solvent may be appropriately set so as to be within the above-described concentration range. By setting the concentration of the benzodioxan compound (3) in the reaction solution within the above range, the amount of the catechol compound (4) obtained in one reaction increases (so-called scale merit occurs). In addition, if the concentration of the benzodioxane compound (3) in the reaction solution is within the above range, the amount of solvent is smaller than that in the prior art, so that the workability of post-treatment can be improved.

When the Lewis acid is AlCl ₃ and the solvent is toluene, the solubility of AlCl _{3 in} the solvent is excellent, and the reaction temperature can be sufficiently increased. The catechol compound (4) can be produced efficiently while reducing. Therefore, the AlCl ₃ and toluene are particularly preferable embodiments as the Lewis acid and the solvent in the second step, respectively.

  The reaction temperature in the second step is usually about 60 to 120 ° C, preferably 80 to 120 ° C, more preferably 100 to 120 ° C.

  The reaction time in the second step is not particularly limited, and the reaction is completed after a part of the reaction solution is sampled to confirm that the benzodioxane compound (3) has disappeared.

  The catechol compound (4) produced by the method of the present invention is purified by applying a known method. For example, the reaction solution is quenched with hydrochloric acid or the like and then extracted with a solvent such as ether, and the solvent is distilled off to obtain a crude organic material. The obtained crude organic substance can be made into a highly pure catechol compound (4) by performing purification such as column chromatography, distillation, sublimation and the like.

  According to the present invention, a benzodioxane compound can be produced more easily and efficiently than a conventional method, and with high purity and high yield. Therefore, the present invention is an excellent method for producing benzodioxane compounds on an industrial scale. Moreover, according to this invention, a catechol compound can be obtained simply and efficiently from the obtained benzodioxane compound.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

Example 1 First Step An external stirring blade, a Dim funnel and a dropping funnel were attached to a 100 mL glass four-necked flask. 1.88 g (13.58 mmol, 0.5 equivalent) of potassium carbonate (special grade of Wako Pure Chemical Industries, Ltd.), 9.57 g (108.66 mmol) of ethylene carbonate (special grade of Kishida Chemical Co., Ltd.) in a four-necked flask at room temperature. 4.0 equivalents) and 14 mL of dimethyl sulfoxide (reagent special grade, Wako Pure Chemical Industries, Ltd.) were added and stirred at 600 rpm. Next, perfluorophenol represented by the following formula from the dropping funnel:

(ZHEJIANG YONGTAI TECHNOLOGY CO, LTD.) 5.00 g (27.17 mmol, 1.0 equivalent) -dimethylsulfoxide 6 mL solution was added dropwise. At this time, the concentration of perfluorophenol with respect to dimethyl sulfoxide was 1.36 mol / L (= 27.17 mmol / (14 mL + 6 mL)). After dropping, the generation of heat and carbon dioxide were confirmed. The reaction solution was heated to 100 ° C. and stirred for 2 hours. After the generation of carbon dioxide could not be confirmed, the reaction solution was further heated to 175 ° C. During the heating, the generation of carbon dioxide was confirmed again from around 120 ° C. A part of the reaction solution is sampled, quenched with hydrochloric acid having a concentration of 1 mol / L, extracted with diisopropyl ether (Kishida Chemical Co., Ltd., special grade), and this extracted solution is gas chromatographed (GC-17A, Shimadzu Corporation, column: DB624). (J & W Scientific) and ¹⁹ F NMR (BRUKER AC-300). After confirming the disappearance of perfluorophenol, the reaction solution was returned to room temperature and quenched with 50 mL of water, and 30 mL of diisopropyl ether was added. The two-phase solution was stirred for 30 minutes and then separated, and the aqueous layer was extracted again with diisopropyl ether (30 mL × twice). All the extracted solutions were mixed, dried over magnesium sulfate (Wako Pure Chemical Industries, Ltd., Chemical), and concentrated using an evaporator (the extracted solution was heated in a 30 ° C. hot water bath under reduced pressure). By purifying the concentrated residue by simple distillation, the target product, perfluorobenzodioxane represented by the following formula:

3.51 g (16.85 mmol, isolated yield 62%) was obtained. The perfluorobenzodioxane was identified using ¹⁹ F NMR and ¹ H NMR (AC-300 manufactured by BRUKER). The physical property values are described below.
¹⁹ F NMR (254 MHz, CDCl ₃ , trifluoromethylbenzene standard, ppm): δ -169.86 to -169.74 (m, 2F), -165.18 to -165.03 (m, 2F)
¹ H NMR (270 MHz, CDCl ₃ , TMS standard, ppm): δ 4.34 (s, 4H)
GC: 19.135min.
Example 2 First Step An external stirring blade, a Dim funnel and a dropping funnel were attached to a 3 L glass 4-neck flask. In a four-necked flask at room temperature, 136.66 g (0.951 mol, 0.5 equivalent) of potassium carbonate (reagent special grade, Wako Pure Chemical Industries, Ltd.), 669.96 g (7.608 mol) of ethylene carbonate (special grade, Kishida Chemical Co., Ltd.) 4.0 equivalents) and 1.0 L of dimethyl sulfoxide (reagent special grade, Wako Pure Chemical Industries, Ltd.) were added and stirred at 600 rpm. Next, 350 g (1.902 mol, 1.0 equivalent) -dimethylsulfoxide 0.4 L solution of perfluorophenol (ZHEJIANG YONGTAI TECHNOLOGY CO, LTD.) Was added dropwise from the dropping funnel. At this time, the concentration of perfluorophenol with respect to dimethyl sulfoxide was 1.36 mol / L (= 1.902 mol / (1.0 L + 0.4 L)). After dropping, the generation of heat and carbon dioxide were confirmed. The reaction solution was heated to 100 ° C. and stirred for 2 hours. After the generation of carbon dioxide could not be confirmed, the reaction solution was further heated to 175 ° C. During the heating, the generation of carbon dioxide was confirmed again from around 120 ° C. A part of the reaction solution is sampled, quenched with hydrochloric acid having a concentration of 1 mol / L and extracted with diisopropyl ether (Kishida Chemical Co., Ltd., special grade). (J & W Scientific) and ¹⁹ F NMR (BRUKER AC-300). After confirming the disappearance of perfluorophenol, the reaction solution was returned to room temperature, quenched with 4 L of water, and 2 L of diisopropyl ether was added. The two-phase solution was stirred for 30 minutes and then separated, and the aqueous layer was extracted again with diisopropyl ether (2 L × 2 times). All the extracted solutions were mixed, dried over magnesium sulfate (Wako Pure Chemical Industries, Ltd., Chemical), and concentrated using an evaporator (the extracted solution was heated in a 30 ° C. hot water bath under reduced pressure). The residue after concentration was purified by simple distillation to obtain 257.29 g (1.236 mol, isolated yield 65%) of perfluorobenzodioxane, which was the target product.

[Example 3] Step 1 The amount of perfluorophenol was 187.09 g (1.016 mol, 1.0 equivalent), and the amount of potassium carbonate was 70.21 g (0.508 mol, 0.5 equivalent). , Except that the amount of ethylene carbonate was 384.89 g (4.371 mol, 4.3 equivalents) and dimethyl sulfoxide was used so that the concentration of perfluorophenol with respect to dimethyl sulfoxide was 1.36 mol / L. In the same manner as in Example 2, 137.43 g (0.660 mol, isolated yield: 65%) of perfluorobenzodioxane, which was the object, was obtained.

[Example 4] First step Instead of 5.00 g of perfluorophenol, 1.97 g (13.33 mmol, 1.0 equivalent) of 2,3,6-trifluorophenol was used, and the amount of potassium carbonate was set to 0.00. The amount of ethylene carbonate was 4.69 g (53.31 mmol, 4.0 equivalent), and the concentration of 2,3,6-trifluorophenol relative to dimethyl sulfoxide was 92 g (6.66 mmol, 0.5 equivalent). Except that dimethyl sulfoxide is used so as to be 1.36 mol / L, it is the target product and is a benzodioxane derivative represented by the following formula:

1.354 g (7.86 mmol, isolated yield 59%) was obtained.

[Example 5] First step 4,5-dimethyl-1,3-dioxolan-2-one represented by the following formula instead of 9.57 g of ethylene carbonate:

The same procedure as in Example 1 was conducted except that 12.62 g (108.66 mmol, 4.0 equivalents) was used and dimethyl sulfoxide was used so that the concentration of perfluorophenol with respect to dimethyl sulfoxide was 1.36 mol / L. Benzodioxane derivatives represented by the following formula:

2.863 g (12.23 mmol, isolated yield 45%) was obtained.

[Example 6] Step 1 The amount of perfluorophenol was 10.0 g (54.33 mmol, 1.0 equivalent), and the amount of potassium carbonate was 3.75 g (27.17 mmol, 0.5 equivalent). , Except that the amount of ethylene carbonate was 9.57 g (108.66 mmol, 2.0 equivalents) and dimethyl sulfoxide was used so that the concentration of perfluorophenol relative to dimethyl sulfoxide was 0.073 mol / L. In the same manner as in Example 1, 4.975 g (23.91 mmol, 44% isolated yield) of the target product perfluorobenzodioxane was obtained.

  The number of equivalents of the phenol compound, base and carbonate compound used in Examples 1 to 6, the concentration of the phenol compound in the solvent, and the yield are shown in the following table.

[Example 7] Second Step An external stirring blade and a Dimroth were attached to a 100 mL glass four-necked flask. At room temperature, aluminum chloride (Wako Pure Chemicals Co., Ltd., Wako Special Grade) 12.81 g (96.12 mmol, 4.0 equivalent), perfluorobenzodioxane 5.00 g (24.03 mmol, 1.0 equivalent) in a 4-neck flask ) And 48 mL of Wako Pure Chemical Industries, Ltd. reagent grade) (concentration of perfluorobenzodioxane to toluene is 0.5 mol / L) and stirred at 600 rpm. The reaction solution was heated and stirred for 2 hours under heating to reflux. A part of the reaction solution was sampled, quenched with hydrochloric acid having a concentration of 1 mol / L, extracted with diisopropyl ether (special grade by Kishida Chemical Co., Ltd.), and the extracted solution was analyzed using gas chromatography and ¹⁹ F NMR. After confirming the disappearance of perfluorobenzodioxane, the reaction solution was returned to room temperature, added to 60 mL of 17.5 wt% hydrochloric acid, and stirred for 1 hour. The two-phase solution was separated, and the toluene layer was extracted with hot water (70 to 80 ° C.) (40 mL × 2 times). The hydrochloric acid and hot water extracted were mixed and extracted again with diisopropyl ether (40 mL × 3 times). The extracted diisopropyl ether solution was dried over magnesium sulfate and concentrated using an evaporator (the extracted solution was heated in a hot water bath at 30 ° C. under reduced pressure). By purifying the concentrated residue by simple distillation or sublimation, the target product is perfluorocatechol represented by the following formula:

2.54 g (13.94 mmol, isolated yield 58%) was obtained.
Perfluorocatechol was identified using ¹⁹ F NMR and ¹ H NMR. The physical property values are described below.
¹⁹ F NMR (254 MHz, CDCl ₃ , trifluoromethylbenzene standard, ppm): δ -169.91 to -169.66 (m, 2F), -165.65 to -165.31 (m, 2F)
¹ H NMR (270 MHz, CDCl ₃ , TMS, ppm): δ 5.33 (s, 2H)
Example 8 Second Step An external stirring blade and a Dimroth were attached to a 3 L glass 4-neck flask. At room temperature, aluminum chloride (Wako Pure Chemical Industries, Ltd. Wako Special Grade) 384.43 g (2.884 mol, 4.0 equivalent), perfluorobenzodioxane 150.00 g (0.721 mol, 1.0 equivalent) in a 4-neck flask ) And toluene (Wako Pure Chemical Industries, Ltd. reagent special grade) 1.442L (concentration of perfluorobenzodioxane to toluene is 0.5 mol / L) and stirred at 600 rpm. The reaction solution was heated and stirred for 2 hours under heating to reflux. A part of the reaction solution was sampled, quenched with hydrochloric acid having a concentration of 1 mol / L, extracted with diisopropyl ether (special grade by Kishida Chemical Co., Ltd.), and the extracted solution was analyzed using gas chromatography and ¹⁹ F NMR. After confirming the disappearance of perfluorobenzodioxane, the reaction solution was returned to room temperature, added to 1.7 L of 17.5 wt% hydrochloric acid, and stirred for 1 hour. The two-phase solution was separated, and the toluene layer was extracted with hot water (70 to 80 ° C.) (1 L × 2 times). The hydrochloric acid and hot water extracted were mixed and extracted again with diisopropyl ether (1 L × 3 times). The extracted diisopropyl ether solution was dried over magnesium sulfate and concentrated using an evaporator (the extracted solution was heated in a hot water bath at 30 ° C. under reduced pressure). The residue after concentration was purified by simple distillation or sublimation to obtain 80.08 g (0.44 mol, isolated yield 61%) of perfluorocatechol as the target product.

[Example 9] Second step Except that the amount of aluminum chloride was 19.22 g (144.18 mmol, 6.0 equivalents), 2.625 g of perfluorocatechol as the target product was obtained in the same manner as in Example 7. (14.42 mmol, isolated yield 60%) was obtained.

[Example 10] Second step Benzodioxane derivative obtained in Example 4 instead of 5.00 g of perfluorobenzodioxane:

Example 7 except that 1.20 g (6.97 mmol, 1.0 eq), the amount of aluminum chloride was 3.72 g (27.89 mmol, 4.0 eq) and the amount of toluene was 14 mL. In the same manner as described above, the catechol compound represented by the following formula:

0.794 g (5.44 mmol, isolated yield 78%) was obtained.

[Example 11] Second step Benzodioxane derivative obtained in Example 5 instead of 5.00 g of perfluorobenzodioxane:

Example 7 except that 2.50 g (10.59 mmol, 1.0 equivalent), the amount of aluminum chloride was 5.65 g (42.34 mmol, 4.0 equivalent), and the amount of toluene was 21 mL. In the same manner as described above, the perfluorocatechol represented by the following formula:

1.253 g (6.88 mmol, isolated yield 65%) was obtained.

[Example 12] Second step The target product was prepared in the same manner as in Example 7, except that 24.08 g (96.12 mmol, 4.0 equivalents) of boron tribromide was used instead of 12.81 g of aluminum chloride. This gave 3.106 g (17.06 mmol, isolated yield 71%) of perfluorocatechol.

[Example 13] Second step The amount of perfluorobenzodioxane was 5.35 g (25.71 mmol, 1.0 equivalent), and the amount of aluminum chloride was 6.86 g (51.42 mmol, 2.0 equivalent). In the same manner as in Example 7 except that the amount of toluene was 51 mL, 1.685 g of perfluorocatechol (9.26 mmol, isolated yield 36%) was obtained.

[Example 14] Second step 1.794 g (9.852) of perfluorocatechol in the same manner as in Example 7 except that the amount of aluminum chloride was changed to 9.61 g (72.09 mmol, 3.0 equivalents). Mmol, isolated yield 41%).

  The chemical formula of the benzodioxane compound used in Examples 7 to 14, the number of equivalents of Lewis acid, the concentration of the benzodioxane compound in the solvent, and the yield are shown in the following table.

Claims (6)

General formula (3):

(In formula, R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are the same or different, respectively, and show a hydrogen atom, a fluorine atom, an alkyl group, or a fluorine-containing alkyl group.
In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group. )
A benzodioxane compound represented by the general formula (1):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
In the presence of a base, the phenol compound represented by general formula (2):

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as above).
The manufacturing method characterized by making it react with the carbonate compound represented by these. ^2. The production method according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom, a fluorine atom or a fluorine-containing alkyl group having 1 to 6 carbon atoms. The production method according to claim 1 or 2, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each is a hydrogen atom or an alkyl group. The manufacturing method in any one of Claims 1-3 made to react in a polar solvent. General formula (4):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group.)
A method for producing a catechol compound represented by:
(I) General formula (1):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
In the presence of a base, the phenol compound represented by general formula (2):

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorine-containing alkyl group.)
Is reacted with a carbonate compound represented by the general formula (3):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as above.)
And (II) reacting the benzodioxane compound with a Lewis acid to produce a benzodioxane compound represented by general formula (4):

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.)
A process for producing a catechol compound represented by:
The manufacturing method characterized by including. The production method according to claim 5, wherein in the step (II), the reaction is performed with an aromatic hydrocarbon solvent.