Method for preparing compounds having cyclic monothiocarbonate groups

Abstract

A method for preparing a compound containing at least one cyclic monothiocarbonate group, comprising reacting a salt of an acidic compound having at least one acidic hydrogen atom with a compound of formula (I) [wherein the group R 1 ~R 4 one of which is a group of formula -AX(II) where A represents an organic group having at least one carbon atom and X represents a halide, and R 1 ~R 4 and the remaining groups independently represent hydrogen or an organic group having 1 to 50 carbon atoms. TIFF2022517403000026.tif32143

Description

[Technical field]

[0001] The object of the present invention is a process for preparing a compound containing at least one cyclic monothiocarbonate group, which comprises reacting a salt of an acidic compound having at least one acidic hydrogen atom with a compound of formula (I):

[0002] [ka] [In the formula, base R 1 ~R 4 One of the formula (II): -AX (wherein A represents an organic group having at least one carbon atom and X represents a halide). is a group of R 1 ~R 4 the remaining groups are each independently hydrogen or an organic group having 1 to 50 carbon atoms. with a compound of formula (I). [Background technology]

[0003] Monothiocarbonate groups provide thiol groups through ring-opening reactions with amino compounds. Thiol groups are highly reactive. Chemical compounds with thiol groups are useful starting materials for chemical synthesis. Polymers with thiol groups can be easily crosslinked or further modified by chemical reactions. Monothiocarbonate groups are latent thiol groups providers. They provide thiol groups through ring-opening reactions when strictly required.

[0004] Thus, compounds bearing a monothiocarbonate group are very useful in chemical synthesis and in technical applications in chemical compounds, such as polymers.

[0005] Different methods for the synthesis of compounds bearing a monothiocarbonate group are described in the state of the art.

[0006] According to the method disclosed in U.S. Pat. No. 3,349,100, alkylene monothiocarbonates are obtained by reacting epoxides with carbonyl sulfide. The availability of carbonyl sulfide is limited. The yield and selectivity of the obtained alkylene monothiocarbonates are low.

[0007] The synthesis using phosgene as starting material is known from US Pat. No. 2,828,318. Phosgene is reacted with hydroxymercaptan. The yield of monothiocarbonate is still low and polymerization by-products are observed.

[0008] The object of US Patents 3,072,676 and 3,201,416 is a two-step process for the preparation of ethylene monothiocarbonate: in the first step, mercaptoethanol and a chlorocarboxylate are reacted to give hydroxyethyl thiocarbonate, which in the second step is heated in the presence of a metal salt catalyst to give ethylene monothiocarbonate.

[0009] According to US Pat. No. 3,517,029, alkylene monothiocarbonates are obtained by reacting mercaptoethanol and a carbonate diester in the presence of a catalytically active salt of thorium.

[0010] Yoichi Taguchi et al., Bull. Chem. Soc. Jpn., 1988, 61, 921-925, disclose the formation of monothiocarbonates by reacting carbon disulfide and 2,2-dimethyloxirane in the presence of trimethylamine.

[0011] Yutaka Nishiyama et al., Tetrahedron, 2006, 62, 5803-5807, disclose the formation of monothiocarbonates using epoxides, sulfur and carbon monoxide as reactants in the presence of sodium hydride.

[0012] M. Luo, X.-H. Zhang and DJ Darensbourg, contribution accepted 13 August 2015, Catalysis Science & Technology, 2015 (DOI: 10.1039 / c5cy00977d), discloses some specific cyclic monothiocarbonates obtained via coupling reactions of carbonyl sulfides with epoxides.

[0013] Etlis, VS and Razuvaev, GA, Doklady Akademi Nauk SSSR, 1962, 142, 838-840 disclose compounds containing cyclic monothiocarbonates substituted with secondary amino groups and their synthesis. However, LA Paquette and LS Wittenbrook, 1966, 31, 1997-1999, do not prepare amino-substituted cyclic monothiocarbonates, but 3-thietane carbamates.

[0014] WO 2019 / 034469 A1 relates to a method for the synthesis of a compound having at least one monothiocarbonate group by reacting a compound having at least one epoxy group with phosgene and subsequently reacting the resulting adduct with an anionic sulfur compound.

[0015] Prior art methods involve the formation of monothiocarbonate ring systems, which are complex and often require the use of hazardous materials such as phosgene. Summary of the Invention [Problem to be solved by the invention]

[0016] It is necessary to have a facile method for introducing monothiocarbonate functionality into other chemical compounds, including polymers, that should be easy to carry out, economical, and not involve the use or formation of any hazardous materials. [Means for solving the problem]

[0017] Thus, a method has been discovered for preparing compounds that include at least one five-membered cyclic monothiocarbonate group.

[0018] In a first aspect, the present invention provides a method for preparing a compound comprising at least one cyclic monothiocarbonate group, comprising reacting a salt of an acidic compound having at least one acidic hydrogen atom with a compound of formula (I):

[0019] [ka] [In the formula, base R 1 ~R 4 One of the formula (II): -AX (wherein A represents an organic group having at least one carbon atom and X represents a halide). is a group of R 1 ~R 4 the remaining groups are each independently hydrogen or an organic group having 1 to 50 carbon atoms. with a compound of formula (I).

[0020] In a further aspect, the present invention provides a salt of an acidic compound selected from hydrogen sulfide or an organic compound containing at least one thiol group, comprising a compound of formula (III):

[0021] [ka] [wherein A is an organic group having at least one carbon atom] with a compound of formula (I).

[0022] In a further aspect, the present invention provides a salt of an organic compound containing at least one imide group, the salt being represented by formula (III):

[0023] [ka] [wherein A is an organic group having at least one carbon atom, preferably an alkylene group having 1 to 10 carbon atoms] with a compound of formula (I). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] A salt of an acidic compound having at least one acidic hydrogen atom Compounds that have an acidic hydrogen atom form salts with bases: the acidic hydrogen dissociates from the compound and adds to the base, resulting in a salt that contains the organic compound as the anion and the base as the cation.

[0025] An acidic hydrogen is, for example, the hydrogen atom of hydrogen sulfide (H2S) or the hydrogen atom of a hydroxyl group, a thiol group, an imide group, a carboxylic acid group, or an acidic carbon-hydrogen group.

[0026] Preferably, the acidic compound is hydrogen sulfide or an organic compound having at least one group selected from a hydroxy group (-OH), a thiol group (-SH), an imide group ((-C(=O)-)2NH), a carboxylic acid group (-COOH) or an acidic carbon-hydrogen group, in particular one in which at least one, preferably both, of the other two substituents on a carbon atom of the acidic carbon-hydrogen group is an electronegative group, such as a carbonyl group or a carboxylic acid group.

[0027] More preferably, the acidic compound is an organic compound having at least one group selected from a hydroxy group (-OH), a thiol group (-SH), an imide group ((-C(=O)-)2NH) or a carboxylic acid group (-COOH).

[0028] In a most preferred embodiment, the acidic compound is an organic compound having at least one group selected from an imide group, alternatively from a thiol group.

[0029] The acidic compound may be a low molecular weight compound or a polymeric compound and may contain, for example, up to 1000, especially up to 500, preferably up to 100 groups selected from hydroxy groups, thiol groups, imide groups, carboxylic acid groups or acidic carbon-hydrogen groups.

[0030] In a preferred embodiment, the acidic compound is an organic compound comprising 1 to 10, in particular 1 to 6, more preferably 1 to 4, and most preferably 1 or 2 groups selected from hydroxy, thiol, imide, carboxylic acid or acidic carbon-hydrogen groups.

[0031] In a preferred embodiment, the organic compound contains either a hydroxy group, a thiol group, an imide group, a carboxylic acid group, or an acidic carbon-hydrogen group, but does not contain any combination thereof.

[0032] The organic compounds may contain additional functional groups and may contain heteroatoms other than oxygen and sulfur. The organic compounds may contain, for example, carbonyl groups, thioether groups, or ether groups.

[0033] In a preferred embodiment, the organic compound does not contain a nitrogen atom in the additional functional group.

[0034] In particularly preferred embodiments, the organic compounds do not contain heteroatoms other than oxygen or sulfur.

[0035] In a more preferred embodiment, the organic compound does not contain any additional functional groups other than carbonyl, thioether or ether groups.

[0036] The organic compounds can be aliphatic or aromatic compounds, or compounds containing both aliphatic and aromatic groups.

[0037] Preferably, the organic compounds have a number average molecular weight Mn, determined by GPC against polystyrene as standard, of up to 1,000,000 g / mol, in particular up to 100,000 g / mol, more preferably up to 10,000 g / mol.

[0038] Particularly preferred organic compounds are non-polymeric compounds having a defined molecular weight of up to 5000 g / mol, especially up to 1000 g / mol.

[0039] Preferred examples of the organic compound are aromatic or aliphatic monohydroxy compounds, or aromatic or aliphatic monothiols, aromatic or aliphatic dihydroxy compounds, or aromatic or aliphatic dithiols.

[0040] The most preferred examples of organic compounds are those having a hydroxy or thiol group directly attached to an aromatic ring system.

[0041] The base can be an organic or inorganic base. Organic bases are, for example, tertiary amines.

[0042] Preferably, the base is an alkali or alkaline earth hydroxide.

[0043] Most preferably, the base is an alkali hydroxide, especially sodium hydroxide or potassium hydroxide.

[0044] An organic compound and a base form a salt, where the organic compound is an anion and the base is a cation.

[0045] Compounds of formula (I) The acidic compounds and base salts are represented by the formula (I):

[0046] [ka] [In the formula, the group R 1 ~R 4 One of the formula (II): -AX where A represents an organic group having at least one carbon atom and X represents a halide, and R 1 ~R 4 the remaining groups are each independently hydrogen or an organic group having 1 to 50 carbon atoms. The compound is reacted with

[0047] The term "halide" as used herein for X is the trivial name for a covalently bonded halogen atom, preferably a Cl atom.

[0048] Preferably, the group R 1 ~R 4 is a group of formula (II), R 1 ~R 4 The remaining radicals are each independently hydrogen or an organic radical having 1 to 10 carbon atoms. The organic radical is preferably a hydrocarbon radical, in particular an alkyl radical.

[0049] More preferably, the group R 1 ~R 4 is a group of formula (II), R 1 ~R 4 The remaining groups are hydrogen.

[0050] Preferably, A is an alkylene group having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, and most preferably, A is methylene.

[0051] Preferably, X is chloride.

[0052] The term "chloride" as used herein for X is the trivial name for a covalently bonded Cl atom.

[0053] Preferably, R 1 is a group of formula (II).

[0054] The most preferred compounds of formula (I) are those of formula (III):

[0055] [ka] in which A has the above meaning, i.e. represents an organic group having at least one carbon atom, preferably A is an alkylene group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, most preferably A is methylene. It is a compound of the formula:

[0056] A most preferred compound of formula (III) is for example 5-(chloromethyl)-1,3-oxathiolan-2-one.

[0057] Synthesis of compounds of formula (I) The compounds of formula (I) are compounds having a five-membered cyclic monothiocarbonate ring system.

[0058] Various methods for the synthesis of compounds bearing a monothiocarbonate ring system are described in the state of the art.

[0059] According to US Patents 3,072,676 and 3,201,416, ethylene monothiocarbonate can be prepared by a two-step process: in the first step, mercaptoethanol and a chlorocarboxylate are reacted to give hydroxyethyl thiocarbonate, which in the second step is heated in the presence of a metal salt catalyst to give ethylene monothiocarbonate.

[0060] According to US Pat. No. 3,517,029, alkylene monothiocarbonates are obtained by reacting mercaptoethanol and a carbonate diester in the presence of a catalytically active salt of thorium.

[0061] According to the method disclosed in U.S. Pat. No. 3,349,100, alkylene monothiocarbonates are obtained by reacting epoxides with carbonyl sulfide. The availability of carbonyl sulfide is limited. The yield and selectivity of the obtained alkylene monothiocarbonates are low.

[0062] The synthesis using phosgene as starting material is known from US Pat. No. 2,828,318. Phosgene is reacted with hydroxymercaptan. The yield of monothiocarbonate is still low and polymerization by-products are observed.

[0063] A preferred method for preparing compounds having a five-membered monothiocarbonate ring system is a) using a compound having an epoxy group (simply called an epoxy compound) as a starting material; b) reacting the compound with phosgene or an alkyl chloroformate, thereby obtaining an adduct; c) The adduct is reacted with a compound containing anionic sulfur to obtain a compound having a five-membered cyclic monothiocarbonate group.

[0064] This method is described in detail in WO 2019 / 034469 A1.

[0065] method In a first step, the salt of an acidic compound and a base can be formed separately and then the resulting salt is reacted with a compound of formula (I).

[0066] Alternatively, an acidic compound can be reacted with a compound of formula (I) in the presence of a base, and the salt is formed in situ. In this alternative, the base is preferably used in an amount of 0.1 to 5 mol, more preferably 0.5 to 2 mol, per mol of the group selected from hydroxy, thiol, imide and carboxylic acid groups.

[0067] Acidic compounds can also be formed in situ; for example, organic compounds having thiol groups can be formed via a Michael addition reaction by reacting hydrogen sulfide with a compound having an unsaturated bond.

[0068] The reaction can be carried out in the presence of a solvent. Suitable solvents are polar solvents, such as dimethylformamide. Ionic liquids can also be used as solvents.

[0069] The acidic compound, respectively hydrogen sulfide or the salt of the organic compound can be reacted in any molar relationship with the compound of formula (I). In order to avoid large amounts of unreacted starting material, 0.5 to 2 moles of the salt, respectively the organic compound can be reacted with 1 mole of the compound of formula (I).

[0070] Preferably, 0.8 to 1.3 mol of the salt, respectively hydrogen sulfide or the organic compound, are reacted with 1 mol of the compound of formula (I).

[0071] The reaction is preferably carried out at elevated temperature, especially at a temperature of from 50 to 150°C.

[0072] The reaction mixture may contain additives such as stabilizers or biocides, for example phenothiazine. Commercially available starting materials may already contain stabilizers or biocides.

[0073] A phase transfer catalyst may be used in the reaction. A suitable phase transfer catalyst may be, for example, a quaternary ammonium salt, such as NMe4Cl.

[0074] In the reaction, no ring opening of the cyclic monothiocarbonate is observed. Instead, a substitution reaction occurs under the formation of the desired compound having at least one cyclic monothiocarbonate group and a salt of a halide. The latter is, for example, sodium chloride when X in formula (II) is a chloride and sodium hydroxide is used as the base. This salt can be separated from the product mixture by conventional means, for example by filtration.

[0075] The product may be further purified, for example by distillation.

[0076] In a further aspect, the present invention provides a salt of an acidic compound selected from hydrogen sulfide or an organic compound containing at least one thiol group, comprising a compound of formula (III):

[0077] [ka] [wherein A is an organic group having at least one carbon atom, preferably an alkylene group having 1 to 10 carbon atoms] with a compound of formula (I).

[0078] The present invention further relates to a compound obtainable by reacting a salt of an acidic compound selected from hydrogen sulfide or an organic compound containing at least one thiol group with 5-(chloromethyl)-1,3-oxathiolan-2-one.

[0079] The present invention further provides a salt of an organic compound containing at least one imide group, the salt being represented by formula (III):

[0080] [ka] [wherein A is an organic group having at least one carbon atom, preferably an alkylene group having 1 to 10 carbon atoms] with a compound of formula (I).

[0081] The present invention further relates to compounds obtainable by reacting a salt of an organic compound containing at least one imide group with 5-(chloromethyl)-1,3-oxathiolan-2-one.

[0082] When hydrogen sulfide is the starting material, the resulting product may have one or two cyclic monothiocarbonate groups, preferably two cyclic monothiocarbonate groups, due to the two acidic hydrogen atoms of hydrogen sulfide.

[0083] When an organic compound is the starting material, the resulting product is an organic compound that is now modified with at least one cyclic monothiocarbonate functionality.

[0084] In the case of organic compounds having hydroxy groups, compounds having ether groups and cyclic monothiocarbonate groups are formed as products.

[0085] In the case of an organic compound having a thiol group, a compound having a thioether group and a cyclic monothiocarbonate group is formed as a product.

[0086] In the case of an organic compound having an imide group, a compound having a substituted imide group and a cyclic monothiocarbonate group is formed as the product.

[0087] In the case of organic compounds having carboxylic acid groups, compounds having ester groups and cyclic monothiocarbonate groups are formed as products.

[0088] Particularly preferred compounds obtainable by the process are those which are prepared by reacting a salt of an organic compound containing at least one thiol group, preferably one or two thiol groups, with a compound of formula (III)

[0089] [ka] and the compound of formula (III) is preferably 5-(chloromethyl)-1,3-oxathiolan-2-one.

[0090] Particularly preferred compounds obtainable by the process also comprise a salt of an organic compound containing at least one imide group, preferably one or two imide groups, of formula (III)

[0091] [ka] and the compound of formula (III) is preferably 5-(chloromethyl)-1,3-oxathiolan-2-one.

[0092] An example of a compound having one thioether group and one cyclic monothiocarbonate group is the following compound:

[0093] [ka]

[0094] A compound having one thioether group and two cyclic monothiocarbonate groups can be obtained by reacting a compound of formula (III) with hydrogen sulfide.

[0095] [ka]

[0096] Examples of compounds having two thioether groups and two cyclic monothiocarbonate groups are:

[0097] [ka] It is.

[0098] An example of a compound having one substituted imide group and one cyclic monothiocarbonate group is the following compound:

[0099] [ka]

[0100] An example of a compound having two substituted imide groups and two cyclic monothiocarbonate groups is the following compound:

[0101] [ka]

[0102] An example of a compound having three substituted imide groups and three cyclic monothiocarbonate groups is the following compound:

[0103] [ka]

[0104] The method of the present invention is a facile way to introduce monothiocarbonate functionality into other chemical compounds, including polymers. The method is economical and does not involve the use or formation of any hazardous materials. The method is highly selective. In the method, no ring-opening reaction of the compound of formula (I) is observed.

[0105] [Example] GC analysis: Agilent Technologies 7890 A Network GC System Column: DB1 (Agilent) 30m, Φ0.25mm, film thickness 1μm Carrier gas: He, flow rate: 1.0 mL / min, split ratio: 50:1 T program: 50℃~300℃, ramp rate 10℃ / min, isotherm 30 min Temperature (injection system) 250℃

[0106] Synthesis Example 5-(chloromethyl)-1,3-oxathiolan-2-one was used as the compound of formula (III). 5-(chloromethyl)-1,3-oxathiolan-2-one was prepared according to WO 2019 / 034469A1 as follows:

[0107] Into a 2 L stirred tank glass reactor equipped with two condensers (-30°C and -78°C (dry ice)), a phosgene dip pipe and an internal thermometer, 594 g (6.41 mol, 1.00 equiv.) of epichlorohydrin was introduced under nitrogen atmosphere. After the starting materials were added, cooling of the tank reactor was started and adjusted to 15°C. After the reactor reached this temperature, 17.8 g (0.0640 mol, 1.00 mol%) of tetrabutylammonium chloride (TBACl) was added. After solvating the TBACl, gaseous phosgene (total 821 g, 8.3 mol, 1.29 equiv.) was added to the reactor via the dip pipe. The temperature of the reaction mixture was continuously monitored and kept below 25°C by carefully adjusting the rate of phosgene addition. The total phosgene addition took approximately 9 hours. After the phosgene addition was complete, the initial cooling of the reactor was discontinued and the reactor was allowed to slowly reach room temperature (approximately 25° C.). The reaction mixture was then stirred at room temperature for 2 hours. Finally, the reaction mixture was stripped phosgene-free with nitrogen overnight at room temperature. The resulting colorless, slightly viscous oil (1214 g, 6.34 mol, 99% yield, regioisomeric purity >95%) was used directly in the thiocarbonate formation without further purification.

[0108] The above β-chloroalkyl chloroformate (50 g) and dichloromethane (50 mL) were each placed in a 500 mL four-neck round bottom flask equipped with a KPG crescent stirrer, dropping funnel, thermometer and reflux condenser. The solution was cooled to 0° C. in an ice bath before slowly adding Na2S (1 equiv., 15 wt % aqueous solution) while maintaining the temperature at 5° C. After the addition was complete, the ice bath was removed and the reaction mixture was allowed to warm to room temperature. After stirring for 2 h, the phases were separated and the aqueous phase was extracted with dichloromethane (2×50 mL). Solvent was removed from the combined organic phase under reduced pressure and the residual liquid was purified by distillation to give the desired cyclic thiocarbonate 5-(chloromethyl)-1,3-oxathiolan-2-one in 77% yield.

[0109] [Example 1]

[0110] [ka]

[0111] Sodium thiophenolate (0.61 g, 5 mmol) was dissolved in dimethylformamide (DMF) (6 g) and 5-(chloromethyl)-1,3-oxathiolan-2-one (0.76 g, 5 mmol) was added. The solution was heated to 120° C. and stirred for 2 h. Based on GC analysis, 75% conversion of 5-(chloromethyl)-1,3-oxathiolan-2-one was achieved, and 5-(phenylsulfanylmethyl)-1,3-oxathiolan-2-one (C 10 H 10 S2O2) in 67% yield. GC-MS analysis: GC (Agilent 7890 A) coupled to MS (Agilent 5975 C) for EI and CI ionization GC column: DB1701, 30m, Φ0.25mm, film thickness 1μm Carrier gas He, flow rate 1.2 mL / min, split ratio 30:1 T program: 50℃~280℃, ramp rate 20℃ / min, isotherm 30 min Temperature (injection system) 250℃ MS / EI mass range: 25-785 amu, ionization energy: 70 eV MS / CI mass range 55~815amu The molecular weight of 226 was determined by EI and CI ionization. The structure of 5-(phenylsulfanylmethyl)-1,3-oxathiolan-2-one was 1 Confirmed by H-NMR (CD2Cl2).

[0112] [Example 2]

[0113] [ka]

[0114] Sodium methacrylate (3.6 g, 33 mmol), tetramethylammonium chloride (0.46 g, 5 mol%) and phenothiazine (5.4 mg, 0.15 wt%) were dissolved in DMF (20 g) and 5-(chloromethyl)-1,3-oxathiolan-2-one (5 g, 33 mmol) was added. The solution was heated to 120° C. and stirred for 4 h. Based on GC analysis, this afforded (2-oxo-1,3-oxathiolan-5-yl)methyl 2-methylprop-2-enoate in 48% yield.

[0115] [Example 3]

[0116] [ka]

[0117] Sodium acetate (2.7 g, 33 mmol) and tetramethylammonium chloride (0.46 g, 5 mol%) were dissolved in DMF (20 g) and 5-(chloromethyl)-1,3-oxathiolan-2-one (5 g, 33 mmol) was added. The solution was heated to 100° C. and stirred for 2 h. Based on GC analysis, this afforded (2-oxo-1,3-oxathiolan-5-yl)methyl-acetate in 23% yield.

[0118] [Example 4]

[0119] [ka]

[0120] Potassium phthalimide (0.93 g, 5 mmol) was dissolved in dimethylformamide (DMF) (6 g) and 5-(chloromethyl)-1,3-oxathiolan-2-one (0.76 g, 5 mmol) was added. The solution was heated to 100° C. and stirred for 3 h. Based on GC analysis, the product was afforded in 22% yield. The following are examples of embodiments of the present invention. [Embodiment 1] A method for preparing a compound containing at least one cyclic monothiocarbonate group, comprising reacting an acidic compound having at least one acidic hydrogen atom and a salt formed with a base with a compound of formula (I):

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Claims

1. A method for preparing a compound containing at least one cyclic monothiocarbonate group, comprising reacting an acidic compound having at least one acidic hydrogen atom and a salt formed with a base with a compound of formula (I): 【Chemistry 1】 [In the formula, base R 1 ~R 4 One of the formula (II): -AX (wherein A represents an organic group having at least one carbon atom and X represents a halide). Based on R 1 ~R 4 the remaining groups independently represent hydrogen or an organic group having 1 to 50 carbon atoms. reacting with a compound of The method, wherein the acidic compound is hydrogen sulfide or an organic compound having at least one group selected from a hydroxy group, a thiol group, an imide group, or a carboxylic acid group.

2. The method of claim 1, wherein the acidic compound is an organic compound having 1 to 10 groups selected from a hydroxy group, a thiol group, an imide group, or a carboxylic acid group.

3. The method of claim 2, wherein the organic compound has a molecular weight of up to 1000 g / mol.

4. 4. The method of claim 2 or 3, wherein the organic compound does not contain heteroatoms other than oxygen or sulfur.

5. 5. The method of claim 2, wherein the organic compound further comprises a carbonyl group, a thioether group or an ether group.

6. 6. The method according to claim 1, wherein the base is an alkali hydroxide.

7. The group R in formula (I) 1 ~R 4 is a group of formula (II), R 1 ~R 4 7. The method of claim 1, wherein the remaining groups are hydrogen.

8. The method according to any one of claims 1 to 7, wherein A in formula (II) is an alkylene group having 1 to 10 carbon atoms.

9. 9. The method of claim 1, wherein X in formula (II) is chloride.

10. The compound of formula (I) may be represented by formula (III): 【Chemistry 2】 [wherein A is an organic group having at least one carbon atom] 10. The method of claim 1, wherein the compound is

11. 11. The method of claim 10, wherein A is an alkylene group having 1 to 10 carbon atoms.

12. 12. The process according to any one of claims 1 to 11, wherein the salts of the acidic compound and the base are formed separately and then the resulting salts are reacted with the compound of formula (I).

13. 12. The process according to any one of claims 1 to 11, wherein an acidic compound is reacted with a compound of formula (I) in the presence of a base, and a salt is formed in situ.

14. The formula: 【Chemistry 3】 Compound.

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