Method for manufacturing sulfur-containing vinyl ethers

Abstract

This invention provides a method for manufacturing a vinyl ether having a sulfur-containing substituent. The method for manufacturing a sulfur-containing vinyl ether according to the following formula (1) of this invention, (in formula (1), R...) 1 and R 2 Each independently represents an alkyldiyl group with 1 to 5 carbon atoms, R 3 Represents an alkyl group with 1 to 5 carbon atoms. n is an integer from 0 to 4. ), The manufacturing method includes the following steps: reacting the compound shown in formula (2) with the compound shown in formula (3) in the presence of a phosphorus compound and an azo compound to obtain the sulfur-containing vinyl ether shown in formula (1), (in formula (2), R 1 and R 2 Each independently represents an alkyldiyl group with 1 to 5 carbon atoms. n is an integer from 0 to 4. ), (in equation (3), R 3 (Refers to alkyl groups with 1 to 5 carbon atoms).

Description

Technical Field

[0001] This invention relates to a method for manufacturing sulfur-containing vinyl ethers. Background Technology

[0002] Vinyl ethers can be used as cationic polymerizable monomers and free radical polymerizable monomers in adhesives, coatings, pharmaceuticals, cosmetics and coating agents. In recent years, people have been developing vinyl ethers with a variety of substituents for the purpose of improving functionality and endowing new properties.

[0003] Regarding vinyl ethers with sulfur-containing substituents, reports of synthetic examples are still very few, indicating that sufficient research has not yet been conducted. For example, Patent Document 1 discloses a method for manufacturing a vinyl ether with sulfur-containing substituents by reacting a halogenated 2-chloroethyl vinyl ether with potassium thioacetate in the presence of triethylamine. However, this method uses a halogenated vinyl ether as a raw material, which may produce toxic gases such as dioxins during combustion, raising concerns about environmental impact. Furthermore, considering the properties of sulfur-containing compounds and their applications in electronic materials such as solid electrolytes, halogen-free materials are required.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2006-48993. Summary of the Invention

[0005] The problem that the invention aims to solve The objective of this invention is to provide a method for manufacturing vinyl ethers having sulfur-containing substituents.

[0006] Solution for solving the problem The inventors conducted repeated and in-depth research and found that by reacting vinyl ethers with thiocarboxylic acids in the presence of phosphorus compounds and azo compounds, vinyl ethers with sulfur-containing substituents can be obtained, thus completing the present invention.

[0007] The present invention includes the following methods.

[0008] [1] The method for manufacturing the sulfur-containing vinyl ether shown in formula (1) below,

Chemistry 1

Chemistry 2

Transformation 3

[0009] [2] The method for manufacturing the sulfur-containing vinyl ether according to formula (1) as described in [1], wherein the phosphorus compound is the compound shown in formula (4) below,

Chemistry 4

[0010] [3] The method for manufacturing sulfur-containing vinyl ethers according to [1] or [2], wherein the azo compound is a compound represented by the following formula (5),

Transformation 5

[0011] [4] A method for manufacturing a sulfur-containing vinyl ether according to any one of [1] to [3], wherein 0.1 to 10 moles of the compound shown in formula (3) are reacted relative to 1 mole of the compound shown in formula (2).

[0012] [5] The method for manufacturing a sulfur-containing vinyl ether according to any one of [1] to [4], wherein the reaction is carried out at a temperature of -50 to 50°C.

[0013] The effects of the invention According to the present invention, it is possible to manufacture sulfur-containing vinyl ethers with low environmental impact that can be used in the synthesis of sulfur-containing vinyl ether polymers, etc.

[0014] Brief description of the attached diagram Figure 1It is the 2-hydroxyethyl vinyl ether (HEVE) used in Example 1 and the 1-{[2-(ethoxy)ethyl]thioalkyl} ethyl-1-one (HEVE-SVE) obtained in Example 1. 1 H-NMR spectrum.

[0015] Figure 2 This is the FT-IR spectrum of 1-{[2-(ethoxy)ethyl]thioalkyl} ethyl-1-one (HEVE-SVE) obtained in Example 1.

[0016] Figure 3 It is the compound (DEGV-SVE) of formula (1-2) obtained in Example 2. 1 H-NMR spectrum and 13 C-NMR spectrum.

[0017] Figure 4 The image shows the FT-IR spectrum of the compound (DEGV-SVE) represented by formula (1-2) obtained in Example 2.

[0018] Figure 5 It is the compound (HBVE-SVE) of formula (1-3) obtained in Example 3. 1 H-NMR spectrum and 13 C-NMR spectrum.

[0019] Figure 6 The image shows the FT-IR spectrum of the compound (HBVE-SVE) represented by formula (1-3) obtained in Example 3. Detailed Implementation

[0020] The present invention will now be described in detail. The description of the present invention described below is sometimes based on suitable embodiments of the invention, but the invention is not limited to such embodiments.

[0021] It should be noted that in this specification, the "~" signifying a numerical range is used to mean that the numerical values ​​described before and after it are the lower and upper limits.

[0022] <Method for manufacturing the sulfur-containing vinyl ether shown in formula (1)> The manufacturing method of the present invention includes a step of reacting the compound shown in formula (2) with the compound shown in formula (3) in the presence of a phosphorus compound and an azo compound to obtain the sulfur-containing vinyl ether shown in formula (1).

[0023] (The compound shown in formula (2)) In the manufacturing method of the present invention, the compound shown in the following formula (2) is used as a raw material.

[0024]

Transformation 6

[0025] In the above formula (2), n is an integer from 0 to 4, preferably from 0 to 3, more preferably from 0 to 2, and even more preferably from 0 to 1.

[0026] Specific examples of compounds represented by formula (2) above include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 4-hydroxybutyl vinyl ether (HBVE), etc.

[0027] (The compound shown in formula (3)) In the manufacturing method of the present invention, the compound shown in the following formula (3) is used as a raw material together with the compound shown in formula (2) above.

[0028]

Transformation 7

[0029] (Phosphorus compounds) In the manufacturing method of the present invention, the compounds shown in formulas (2) and (3) above are reacted in the presence of a phosphorus compound and an azo compound. The phosphorus compound is not particularly limited; for example, one or more compounds shown in formula (4) below may be used.

[0030]

Transformation 8

[0031] The aforementioned alkyl group can be any of the following: straight-chain, branched, and cyclic. Examples of such alkyl groups include straight-chain 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.

[0032] Specific examples of compounds represented by formula (4) above include tri-n-butylphosphine, tri-tert-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, diethylphenylphosphine, isopropyl diphenylphosphine, tricyclohexylphosphine, dicyclohexylphenylphosphine, phenoxy diphenylphosphine, and triphenylphosphine (Ph3P). Among these, from the viewpoint of oxygen affinity, tri-n-butylphosphine and triphenylphosphine (Ph3P) are preferred.

[0033] (Azo compounds) As an azo compound, there are no particular limitations; for example, one or more compounds represented by the following formula (5) may be used.

[0034]

Chemistry 9

[0035] The alkyl group of the aforementioned alkoxy group can be any of straight-chain, branched, or cyclic, and may also have substituents. Examples of such alkyl groups include straight-chain 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 for the alkyl group include halogen atoms, alkoxy groups, phenyl groups, amino groups, hydroxyl groups, carboxyl groups, and sulfonyl groups; examples of alkoxy groups include methoxy, ethoxy, n-propoxy, and isopropoxy. The aforementioned amino group may also be replaced by one or two alkyl groups having 1 to 6 carbon atoms, such as methylamino, ethylamino, dimethylamino, diethylamino, or methylethyl.

[0036] Specific examples of compounds represented by formula (5) above include dimethyl azodicarbonate, diethyl azodicarbonate, diisopropyl azodicarbonate (DIAD), di-tert-butyl azodicarbonate, di(2-methoxyethyl) azodicarbonate, dibenzyl azodicarbonate, di(2,2,2-trichloroethyl) azodicarbonate, 1,1'-azobis(N,N-dimethylformamide), and 1,1'-(azodicarbonyl)dipiperidine. Among these, diethyl azodicarbonate and diisopropyl azodicarbonate (DIAD) are preferred from the viewpoint of hydrogen affinity.

[0037] The reaction between the compound shown in formula (2) and the compound shown in formula (3) is preferably carried out in an organic solvent. Examples of organic solvents include ethyl acetate, dichloromethane, tetrahydrofuran (THF), acetone, acetonitrile, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), among which tetrahydrofuran (THF) and acetonitrile are preferred.

[0038] The amount of phosphorus compound used is preferably 0.1 to 10 moles relative to 1 mole of the compound shown in formula (2) above, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles.

[0039] The amount of azo compound used is preferably 0.1 to 10 moles relative to 1 mole of the compound shown in formula (2) above, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles.

[0040] The amount of the compound shown in formula (3) used relative to 1 mole of the compound shown in formula (2) is preferably 0.1 to 10 moles, more preferably 0.2 to 5 moles, and even more preferably 0.5 to 2 moles.

[0041] There are no particular restrictions on the reaction conditions between the compound shown in formula (2) and the compound shown in formula (3). For example, the reaction temperature is preferably -30 to 30°C, more preferably -20 to 20°C, and the reaction time is about 6 to 24 hours.

[0042] (The vinyl ether shown in formula (1)) The vinyl ether with sulfur-containing substituents obtained by the above reaction has the structure shown in the following formula (1).

[0043]

Chemistry 10

[0044] As specific examples of the vinyl ethers shown in formula (1) above, the compounds shown in (1-1) to (1-3) below can be cited.

[0045]

Chemistry 11

[0046] For example, saturated saline solution is added to the reaction solution for separation, the vinyl ether of formula (1) contained in the organic layer is recovered, and the organic solvent contained in the organic layer is removed by vacuum distillation, etc. Then, it can be cleaned, dried and treated as needed.

[0047] The sulfur-containing vinyl ether obtained as shown in formula (1) above can be used as a cationic polymerizable monomer and a free radical polymerizable monomer in, for example, coatings, pharmaceuticals, cosmetics, coating agents, electrolyte materials, self-healing materials, etc. Example

[0048] The present invention will be described in detail below through examples, but the present invention is not limited thereto.

[0049] <Example 1> Add 101.6 g (0.388 mol) triphenylphosphine (Ph3P), 80 mL (0.406 mol) diisopropyl azodicarbonate (DIAD), and 500 mL tetrahydrofuran (THF) to a 1000 mL four-necked flask and stir. Then, while stirring, lower the temperature to 0 °C, add 31.4 mL (0.35 mol) 2-hydroxyethyl vinyl ether (HEVE) and 29.4 mL (0.408 mol) thioacetic acid (AcSH), and stir overnight. After stirring, separate the layers with 500 mL saturated sodium bicarbonate solution and recover the organic layer. Remove the organic solvent from the organic layer by vacuum distillation using an evaporator, add 100 mL dichloromethane, wash five times with 20 mL water, and separate the layers to recover the organic layer. Sodium sulfate was added to the organic layer and dried, and then vacuum distilled to obtain 1-{[2-(ethoxy)ethyl]thioalkyl} ethyl-1-one (HEVE-SVE) as shown in formula (1-1).

[0050]

Chemistry 12

[0051]

Chemistry 13

[0052] As a result of the analysis, the obtained vinyl ether was confirmed to be the compound (HEVE-SVE) shown in (1-1) above.

[0053] <Example 2> In a round-bottom flask equipped with a reflux condenser, 50.8 g (0.194 mol) of triphenylphosphine (Ph3P), 250 mL of tetrahydrofuran (THF), and 40 mL (0.203 mol) of diisopropyl azodicarbonate (DIAD) were added. The mixture was then stirred at room temperature for approximately 8 hours until heating 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 the mixture was stirred overnight. After stirring, the reaction mixture was evaporated to remove THF, and the solids were removed by filtration. Approximately 100 mL of dichloromethane was added to the resulting filtrate, and the mixture was washed three times with 100 mL of water. After washing, the mixture was distilled under reduced pressure at 150 °C and 0.06 kPa to give the compound (DEGV-SVE) shown in formula (1-2) (yield ~50%). The resulting DEGV-SVE was a pink liquid.

[0054]

Chemistry 14

[0055]

Chemistry 15

[0056] As a result of the analysis, the obtained vinyl ether was confirmed to be the compound shown in (1-2) above.

[0057] <Example 3> 101.6 g (0.388 mol) of triphenylphosphine (Ph3P), 500 mL of tetrahydrofuran (THF), and 80 mL (0.406 mol) of diisopropyl azodicarbonate (DIAD) were added to a round-bottom flask equipped with a reflux condenser. The mixture was then stirred at room temperature for approximately 8 hours until heating ceased. Next, 40.7 mL (0.35 mol) of 4-hydroxybutylvinyl 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 THF, and the solids were removed by filtration. Approximately 120 mL of dichloromethane was added to the resulting filtrate, and the mixture was washed three times with 100 mL of water. After washing, the mixture was distilled under reduced pressure at 150 °C and 0.1 kPa to give the compound (HBVE-SVE) shown in formulas (1-3) (yield ~70%). The resulting HBVE-SVE is a pink liquid.

[0058]

Chemistry 16

[0059]

Chemistry 17

[0060] As a result of the analysis, the obtained vinyl ether was confirmed to be the compound (HBVE-SVE) shown in (1-3) above.

Claims

1. A method for manufacturing the sulfur-containing vinyl ether shown in formula (1) below, In equation (1), R 1 and R 2 Each independently represents an alkyldiyl group with 1 to 5 carbon atoms, R 3 Represents alkyl groups with 1 to 5 carbon atoms, where n is an integer from 0 to 4. The manufacturing method includes the following steps: reacting the compound represented by formula (2) with the 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). In equation (2), R 1 and R 2 Each alkane group independently represents an alkane group with 1 to 5 carbon atoms, where n is an integer from 0 to 4; In equation (3), R 3 Indicates an alkyl group having 1 to 5 carbon atoms.

2. The method for manufacturing sulfur-containing vinyl ethers according to claim 1 or 2, wherein, The phosphorus compound is a compound represented by the following formula (4). In equation (4), R 4 R 5 and R 6 Each can independently represent an alkyl, phenyl, or phenoxy group having 1 to 8 carbon atoms.

3. The method for manufacturing sulfur-containing vinyl ethers according to claim 1 or 2, wherein, The azo compound is a compound represented by the following formula (5). In equation (5), R 7 It indicates alkoxy, amino, or piperidinyl.

4. The method for manufacturing sulfur-containing vinyl ethers according to claim 1 or 2, wherein, Relative to 1 mole of the compound represented by formula (2), react 0.1 to 10 moles of the compound represented by formula (3).

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

Images