Method for producing sulfur-containing vinyl ether

Abstract

The present invention provides a method for producing vinyl ether having a sulfur-containing substituent. This method for producing sulfur-containing vinyl ether represented by formula (1) (wherein R1 and R2 each independently represent a C1-5 alkanediyl group, R3 represents a C1-5 alkyl group, and n is an integer of 0-4) comprises a step for obtaining sulfur-containing vinyl ether represented by formula (1) by reacting a compound represented by formula (2) (wherein R1 and R2 each independently represent a C1-5 alkanediyl group, and n is an integer of 0-4) and a compound represented by formula (3) (wherein R3 represents a C1-5 alkyl group) in the presence of a phosphorus compound and an azo compound.

Description

Method for producing sulfur-containing vinyl ethers

[0001] The present invention relates to a method for producing sulfur-containing vinyl ethers.

[0002] Vinyl ethers are used as cationically polymerizable monomers or radically polymerizable monomers in adhesives, paints, pharmaceuticals, cosmetics, coating agents, and the like. In recent years, vinyl ethers having various substituents have been developed with the aim of improving functionality or imparting new properties.

[0003] Among these, there have been very few reports of synthesis examples of vinyl ethers having sulfur-containing substituents, and the reality is that they have not yet been fully studied. For example, Patent Document 1 discloses a method for producing vinyl ethers having sulfur-containing substituents by reacting 2-chloroethyl vinyl ether having a halogen substituent with potassium thioacetate in the presence of triethylamine. However, since this production method uses a vinyl ether containing a halogen as a raw material, there is a risk of generating toxic gases such as dioxins upon combustion, raising concerns about the impact on the environment. Furthermore, when considering the application of the properties of sulfur-containing compounds to electronic materials such as solid electrolytes, halogen-free materials are required.

[0004] Japanese Patent Application Laid-Open No. 2006-48993

[0005] An object of the present invention is to provide a method for producing vinyl ethers having sulfur-containing substituents.

[0006] As a result of extensive research, the present inventors have found that a vinyl ether having a sulfur-containing substituent can be obtained by reacting a vinyl ether having a specific structure with a thiocarboxylic acid in the presence of a phosphorus compound and an azo compound, and have thus completed the present invention.

[0007] The present invention includes the following aspects: [1] A compound represented by the following formula (1): (In formula (1), R １ and R ２ each independently represents an alkanediyl group having 1 to 5 carbon atoms; R ３represents an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 4. (In formula (2), R １ and R ２ each independently represents an alkanediyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 4. (In formula (3), R ３ represents an alkyl group having 1 to 5 carbon atoms) in the presence of a phosphorus compound and an azo compound to obtain a sulfur-containing vinyl ether represented by formula (1).

[0008] [2] The method for producing a sulfur-containing vinyl ether represented by formula (1) according to [1], wherein the phosphorus compound is a compound represented by the following formula (4): (In formula (4), R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenoxy group.) [3] The method for producing a sulfur-containing vinyl ether according to [1] or [2], wherein the azo compound is a compound represented by the following formula (5): (In formula (5), R ７ represents an alkoxy group, an amino group, or a piperidyl group.) [4] The method for producing a sulfur-containing vinyl ether according to any one of [1] to [3], in which 0.1 to 10 moles of a compound represented by formula (3) are reacted with 1 mole of a compound represented by formula (2). [5] The method for producing a sulfur-containing vinyl ether according to any one of [1] to [4], in which the reaction is carried out at -50 to 50°C.

[0009] According to the present invention, it is possible to produce a sulfur-containing vinyl ether which has a low environmental impact and can be used for synthesizing a sulfur-containing vinyl ether polymer, etc.

[0010] FIG. 1 shows the structure of 2-hydroxyethyl vinyl ether (HEVE) used in Example 1 and 1-{[2-(ethenyloxy)ethyl]sulfanyl}ethan-1-one (HEVE-SVE) obtained in Example 1. １1H-NMR spectrum. FIG. 2 is an FT-IR spectrum of 1-{[2-(ethenyloxy)ethyl]sulfanyl}ethan-1-one (HEVE-SVE) obtained in Example 1. FIG. 3 is an FT-IR spectrum of the compound (DEGV-SVE) represented by formula (1-2) obtained in Example 2. １ H-NMR spectrum and １３ FIG. 4 is a C-NMR spectrum of the compound (DEGV-SVE) represented by formula (1-2) obtained in Example 2. FIG. 5 is a FT-IR spectrum of the compound (HBVE-SVE) represented by formula (1-3) obtained in Example 3. １ H-NMR spectrum and １３ 6 is a C-NMR spectrum of the compound (HBVE-SVE) obtained in Example 3 and represented by formula (1-3).

[0011] The present invention will be described in detail below. The following description of the present invention may be based on preferred embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the term "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits.

[0012] <Method for producing sulfur-containing vinyl ether represented by formula (1)> The production method of the present invention includes a step of reacting a compound represented by formula (2) with a compound represented by formula (3) in the presence of a phosphorus compound and an azo compound to obtain the sulfur-containing vinyl ether represented by formula (1).

[0013] (Compound Represented by Formula (2)) In the production method of the present invention, a compound represented by the following formula (2) is used as a raw material. In the above formula (2), R １ and R ２ each independently represents an alkanediyl group having 1 to 5 carbon atoms. Examples of the alkanediyl group include a methylene group (—CH ２ -), ethylene group (-CH ２ -CH ２ -), propylene group (-CH ２ -CH ２ -CH ２-), butylene group (-CH ２ -CH ２ -CH ２ -CH ２ The alkanediyl group preferably has 1 to 4 carbon atoms.

[0014] In the above formula (2), n is an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1.

[0015] Specific examples of the compound represented by the above formula (2) include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), and 4-hydroxybutyl vinyl ether (HBVE).

[0016] (Compound Represented by Formula (3)) In the production method of the present invention, a compound represented by the following formula (3) is used as a raw material together with the compound represented by the above formula (2). In the above formula (3), R ３ represents an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R ３ The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.

[0017] (Phosphorus Compound) In the production method of the present invention, the compounds represented by the above formulas (2) and (3) are reacted in the presence of a phosphorus compound and an azo compound. The phosphorus compound is not particularly limited, and for example, one or more compounds represented by the following formula (4) can be used: In the above formula (4), R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenoxy group.

[0018] The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0019] Specific examples of the compound represented by the above formula (4) include tri-n-butylphosphine, tri-tert-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, diethylphenylphosphine, isopropyldiphenylphosphine, tricyclohexylphosphine, dicyclohexylphenylphosphine, phenoxydiphenylphosphine, triphenylphosphine (Ph ３ Among these, tri-n-butylphosphine, triphenylphosphine (Ph ３ P) is preferred.

[0020] (Azo Compound) The azo compound is not particularly limited, and for example, one or more compounds represented by the following formula (5) can be used. In the above formula (5), R ７ represents an alkoxy group, an amino group, or a piperidyl group.

[0021] The alkyl group of the alkoxy group may be linear, branched, or cyclic, and may have a substituent. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. The alkyl group preferably has 1 to 8 carbon atoms. Examples of substituents on the alkyl group include halogen atoms, alkoxy groups, phenyl, amino, hydroxy, carboxy, and sulfo groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, and isopropoxy groups. The amino group may be substituted with one or two alkyl groups having 1 to 6 carbon atoms, such as methylamino, ethylamino, dimethylamino, diethylamino, and methylethyl.

[0022] Specific examples of the compound represented by formula (5) include dimethyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate (DIAD), di-tert-butyl azodicarboxylate, bis(2-methoxyethyl) azodicarboxylate, dibenzyl azodicarboxylate, bis(2,2,2-trichloroethyl) azodicarboxylate, 1,1'-azobis(N,N-dimethylformamide), 1,1'-(azodicarbonyl)dipiperidine, etc. Among these, diethyl azodicarboxylate, diisopropyl azodicarboxylate (DIAD), etc. are preferred from the viewpoint of hydrogen affinity.

[0023] The reaction between the compound represented by formula (2) and the compound represented by formula (3) is preferably carried out in an organic solvent, such as ethyl acetate, dichloromethane, tetrahydrofuran (THF), acetone, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc., and among these, tetrahydrofuran (THF), acetonitrile, etc. are preferred.

[0024] The amount of the phosphorus compound used is preferably 0.1 to 10 moles, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles, per mole of the compound represented by the formula (2).

[0025] The amount of the azo compound used is preferably 0.1 to 10 moles, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles, per mole of the compound represented by formula (2).

[0026] The amount of the compound represented by formula (3) used is preferably 0.1 to 10 moles, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles, per mole of the compound represented by formula (2).

[0027] The reaction conditions for the compound represented by formula (2) and the compound represented by formula (3) are not particularly limited. For example, the reaction temperature is preferably −30 to 30° C., more preferably −20 to 20° C., and the reaction may be carried out for about 6 to 24 hours.

[0028] (Vinyl Ether Represented by Formula (1)) The vinyl ether having a sulfur-containing substituent obtained by the above reaction has a structure represented by the following formula (1). In the above formula (1), R １ and R ２ R each independently represents an alkanediyl group having 1 to 5 carbon atoms, and the alkanediyl group preferably has 1 to 4 carbon atoms. ３ represents an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R ３ The number of carbon atoms in the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. n is an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0029] Specific examples of the vinyl ether represented by the above formula (1) include the compounds represented by the following (1-1) to (1-3).

[0030] In the production method of the present invention, the sulfur-containing vinyl ether represented by formula (1) obtained by the reaction may be further purified, if necessary. Examples of the purification method include separation, filtration, washing, drying, distillation, chromatography, membrane separation, etc., and one or more of these may be used.

[0031] For example, saturated saline or the like may be added to the reaction solution to separate the liquids, and the vinyl ether represented by formula (1) contained in the organic layer may be recovered. Thereafter, the organic solvent contained in the organic layer may be removed by vacuum distillation or the like, and further, if necessary, the organic layer may be subjected to treatments such as washing and drying.

[0032] The sulfur-containing vinyl ether represented by formula (1) obtained as described above can be used as a cationically polymerizable monomer or a radically polymerizable monomer in, for example, paints, pharmaceuticals, cosmetics, coating agents, electrolyte materials, self-repairing materials, etc.

[0033] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0034] Example 1 In a 1000 mL four-neck flask, 101.6 g (0.388 mol) of triphenylphosphine (Ph ３ P), 80 mL (0.406 mol) diisopropyl azodicarboxylate (DIAD), and 500 mL tetrahydrofuran (THF) were added and stirred. Thereafter, the temperature was lowered to 0°C while stirring, and 31.4 mL (0.35 mol) 2-hydroxyethyl vinyl ether (HEVE) and 29.4 mL (0.408 mol) thioacetic acid (AcSH) were added and stirred overnight. After stirring, the mixture was separated with 500 mL saturated aqueous sodium bicarbonate and the organic layer was recovered. The organic solvent contained in the organic layer was removed under reduced pressure using an evaporator, and then 100 mL of dichloromethane was added, and the mixture was washed and separated five times with 20 mL of water, and the organic layer was recovered. Sodium sulfate was added to the organic layer to dry it, and then distilled under reduced pressure to obtain 1-{[2-(ethenyloxy)ethyl]sulfanyl}ethan-1-one (HEVE-SVE) represented by the following formula (1-1).

[0035]

[0036] The reaction formula for the above reaction is shown below.

[0037] The vinyl ether obtained by the above reaction was dissolved in deuterated chloroform (CDCl ３ ) and dissolved in a solvent, and analyzed using an NMR apparatus (JNM-ECX500II, manufactured by JEOL) under the condition of a magnetic field strength of 600 MHz. １ H-NMR measurement was carried out. １ H-NMR spectrum was obtained. ２ O) Dissolve in a solvent and １ H-NMR measurements were carried out. The results are shown in Figure 1. Furthermore, the vinyl ether obtained by the reaction was subjected to Fourier transform infrared absorption spectroscopy (FT-IR) measurements. For the FT-IR measurements, an FTS-3000 manufactured by Varian was used. The results are shown in Figure 2. Furthermore, DART mass spectrometry (JMS-T100LP AccuTOF ＴＭ LC-Express (manufactured by JEOL Co., Ltd.) was performed. ６ H １１ O ２ S+H ＋ A signal of 147.0479 Da (calculated value 147.0474 Da) corresponding to the mass of

[0038] As a result of analysis, it was confirmed that the obtained vinyl ether was the compound (HEVE-SVE) represented by the above formula (1-1).

[0039] Example 2: In a round-bottom flask equipped with a reflux condenser, 50.8 g (0.194 mol) of triphenylphosphine (Ph ３P), 250 mL of tetrahydrofuran (THF), and 40 mL (0.203 mol) of diisopropyl azodicarboxylate (DIAD) were added. The mixture was then stirred at room temperature for approximately 8 hours until the heat generation ceased. Next, 22.52 mL (0.175 mol) of diethylene glycol monovinyl ether (DEGV) and 14.6 mL (0.204 mol) of thiosulfate (AcSH) were added at 0°C and stirred overnight. After stirring, the reaction mixture was evaporated to remove the THF, and the solids were removed by suction filtration. Approximately 100 mL of dichloromethane was added to the obtained filtrate, and the mixture was washed with 100 mL of water three times. After washing, the mixture was distilled under reduced pressure at 150°C and 0.06 kPa to obtain the compound (DEGV-SVE) represented by the following formula (1-2) (yield: 50%). The obtained DEGV-SVE was a pink liquid.

[0040]

[0041] The reaction formula for the above reaction is shown below.

[0042]

[0043] The vinyl ether obtained by the above reaction was subjected to the same procedure as in Example 1. １ H-NMR measurement was carried out. １ H-NMR spectrum was obtained. ３ ) dissolved in a solvent, and subjected to NMR analysis using the same NMR apparatus as in Example 1 under the condition of a magnetic field strength of 125 MHz. １３ C-NMR measurement was carried out. １３ A C-NMR spectrum was obtained. The results are shown in Figure 3. Furthermore, FT-IR measurement was carried out on the above vinyl ether in the same manner as in Example 1. The results are shown in Figure 4. Furthermore, DART mass spectrometry (JMS-T100LP AccuTOF ＴＭ LC-Express (manufactured by JEOL Co., Ltd.) was performed. ８ H １４ O ３ S+H ＋ A signal of 191.0735 Da (calculated value 191.0736 Da) corresponding to the mass of

[0044] As a result of analysis, it was confirmed that the obtained vinyl ether was the compound represented by (1-2) above.

[0045] Example 3: In a round-bottom flask equipped with a reflux condenser, 101.6 g (0.388 mol) of triphenylphosphine (Ph ３ P), 500 mL of tetrahydrofuran (THF), and 80 mL (0.406 mol) of diisopropyl azodicarboxylate (DIAD) were added. The mixture was then stirred at room temperature for approximately 8 hours until the heat generation ceased. Next, 40.7 mL (0.35 mol) of 4-hydroxybutyl vinyl ether (HBVE) and 29.2 mL (0.408 mol) of thioacetic acid (AcSH) were added, and the mixture was stirred overnight at 0°C. After stirring, the reaction mixture was evaporated to remove the THF, and the solids were removed by suction filtration. Approximately 120 mL of dichloromethane was added to the resulting filtrate, and the mixture was washed with 100 mL of water three times. After washing, the mixture was distilled under reduced pressure at 150°C and 0.1 kPa to obtain a compound (HBVE-SVE) represented by the following formula (1-3) (yield: 70%). The resulting HBVE-SVE was a pink liquid.

[0046]

[0047] The reaction formula for the above reaction is shown below.

[0048]

[0049] The vinyl ether obtained by the above reaction was subjected to the same procedures as in Examples 1 and 2. １ H-NMR measurement, １３ C-NMR and FT-IR measurements were carried out. The results are shown in Figures 5 and 6, respectively. DART mass spectrometry was also carried out. ８ H １４ O ２ S+H ＋ A signal of 175.0782 Da (calculated value 175.0787 Da) corresponding to the mass of

[0050] As a result of analysis, it was confirmed that the obtained vinyl ether was the compound (HBVE-SVE) represented by the above formula (1-3).

Claims

1. The following formula (1) (In formula (1), R １ and R ２ each independently represents an alkanediyl group having 1 to 5 carbon atoms; R ３ represents an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 4. (In formula (2), R １ and R ２ each independently represents an alkanediyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 4. (In formula (3), R ３ represents an alkyl group having 1 to 5 carbon atoms) in the presence of a phosphorus compound and an azo compound to obtain a sulfur-containing vinyl ether represented by formula (1).

2. The method for producing a sulfur-containing vinyl ether according to claim 1 or 2, wherein the phosphorus compound is a compound represented by the following formula (4): (In formula (4), R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenoxy group.

3. The method for producing a sulfur-containing vinyl ether according to claim 1 or 2, wherein the azo compound is a compound represented by the following formula (5): (In formula (5), R ７ represents an alkoxy group, an amino group, or a piperidyl group.

4. The method for producing a sulfur-containing vinyl ether according to claim 1 or 2, wherein 0.1 to 10 moles of the compound represented by formula (3) are reacted with 1 mole of the compound represented by formula (2).

5. The method for producing a sulfur-containing vinyl ether according to claim 1 or 2, wherein the reaction is carried out at a temperature of -50 to 50°C.

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