Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
  • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods

Definitions

• the present invention relates to a method for producing a dicarboxylic acid monoester and a dicarboxylic acid monoester salt.
• Optical films such as optical compensatory sheets and retardation films are used in various image display devices in order to eliminate image coloring and widen the viewing angle.
• a stretched birefringent film has been used as an optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystalline compound instead of the stretched birefringent film.
• the liquid crystalline compound used for forming such an optically anisotropic layer includes, for example, a hydroxy compound for forming a skeleton located in the center of the molecule of the liquid crystalline compound and a side chain portion for forming a side chain portion of the liquid crystalline compound. It is known to synthesize using a carboxylic acid compound of and an esterification reaction of . As a method for synthesizing the carboxylic acid compound, for example, Patent Document 1 describes a method for synthesizing a dicarboxylic acid monoester from a dicarboxylic acid ([0092] [0093]).
• the present inventors investigated the method for synthesizing the dicarboxylic acid monoester described in Patent Document 1, and found that, depending on the reaction conditions, a dicarboxylic acid dimonoester was also produced as a by-product. It was clarified that there is room for improvement in the selectivity of esters.
• an object of the present invention is to provide a method for producing a dicarboxylic acid monoester with excellent selectivity for the dicarboxylic acid monoester and a novel dicarboxylic acid monoester salt.
• the present inventors have found that adopting a reaction system using a base in a protic solvent improves the selectivity of the dicarboxylic acid monoester. perfected the invention. That is, the inventors have found that the above object can be achieved by the following configuration.
• a dicarboxylic acid represented by the formula (1) described later and an alcohol derivative represented by the formula (2) described later are reacted in a protic solvent using a base to obtain the formula (3) described later.
• a method for producing a dicarboxylic acid monoester which produces a dicarboxylic acid monoester represented by (4).
• the base is an inorganic base.
• the dicarboxylic acid represented by the formula (1) described later is a compound represented by the formula (1-1) described later, [1] to [ 6].
• the dicarboxylic acid monoester according to any one of [1] to [8], wherein the dicarboxylic acid monoester represented by formula (3) described later is a compound represented by formula (3-2) described later.
• a method for producing an acid monoester [10]
• each component may use the substance applicable to each component individually by 1 type, or may use 2 or more types together.
• the content of the component refers to the total content of the substances used in combination unless otherwise specified.
• the method for producing a dicarboxylic acid monoester of the present invention comprises a dicarboxylic acid represented by the following formula (1) and a dicarboxylic acid represented by the following formula (2). and an alcohol derivative in a protic solvent using a base to produce a dicarboxylic acid monoester represented by the following formula (3) or (4).
• the explanations in the following formulas (1) to (4) will be detailed later.
• the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) are reacted using a base in a protic solvent,
• the selectivity of the dicarboxylic acid monoester can be improved.
• the present inventors presume as follows. That is, in the present invention, considering that the produced dicarboxylic acid monoester is precipitated from the reaction solvent, by using a protic solvent as the reaction solvent, both ends of the dicarboxylic acid are dissociated by a base.
• the dicarboxylic acid used in the production method of the present invention is a dicarboxylic acid represented by the following formula (1).
• W is a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a divalent hydrocarbon group having 6 to 20 carbon atoms, An aromatic hydrocarbon group, a divalent heterocyclic group having 2 to 20 carbon atoms, or two or more same or different groups selected from the group consisting of these groups linked by a single bond or a divalent linking group represents a group.
• the hydrogen atom contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the heterocyclic group is a halogen atom, —R w1 , —OR w1 , cyano group or nitro R w1 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
• the divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms represented by one aspect of W includes, for example, groups represented by the following formulas (W-7) to (W-19) is mentioned.
• Examples of the divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms represented by one aspect of W include groups represented by the following formulas (W-1) to (W-6).
• Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by one aspect of W include groups represented by the following formulas (W-20) to (W-27).
• the divalent heterocyclic group having 2 to 20 carbon atoms represented by one aspect of W may be either aromatic or non-aromatic. is preferably an aromatic heterocyclic group.
• Atoms other than carbon constituting the divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom.
• the aromatic heterocyclic group has a plurality of non-carbon ring-constituting atoms, these may be the same or different.
• divalent aromatic heterocyclic groups include, for example, pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group ), isoquinolylene group (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group , thiazolothiazole-diyl group, thienothiophene-diyl group, and thienooxazole-diyl group.
• pyridylene group pyridine-diy
• W in the above formula (1) is, as described above, a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a 6 to 20 carbon atoms and two or more groups of the same or different type selected from the group consisting of a divalent aromatic hydrocarbon group and a divalent heterocyclic group having 2 to 20 carbon atoms linked by a single bond or a divalent linking group may be a group.
• two or more groups of the same kind refer to, for example, two or more groups selected from divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms.
• divalent linking groups means, for example, two or more groups selected from each of a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms.
• R 11 to R 16 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.
• W in the above formula (1) preferably has a ring structure.
• W in the above formula (1) is the above-described divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and It is preferably a group in which two or more same or different groups selected from the group consisting of divalent heterocyclic groups having 2 to 20 carbon atoms are linked by a single bond or a divalent linking group, and has 3 carbon atoms.
• the dicarboxylic acid represented by the above formula (1) is preferably a compound represented by the following formula (1-1) because the optical properties of the resulting film are good.
• R 1 and R 2 each independently represent a ring structure.
• L 1 represents a single bond or a divalent linking group.
• n represents an integer of 0 to 2. However, when n represents 2, the plurality of R 2 and L 1 may be the same or different.
• the ring structures represented by R 1 and R 2 in the above formula (1-1) are the above-mentioned divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. It is not particularly limited as long as it is a ring structure contained in a hydrogen group and a divalent heterocyclic group having 2 to 20 carbon atoms.
• Examples of the ring structure include aromatic hydrocarbon rings, aromatic heterocyclic rings, aliphatic hydrocarbon rings, and aliphatic heterocyclic rings, which may have substituents.
• aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthroline rings.
• aromatic heterocyclic ring include furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothiazole ring.
• aliphatic hydrocarbon ring examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, a cyclodocosane ring, and the like.
• aliphatic heterocycles include pyrrolidine, oxolane, thiolane, piperidine, oxane, thiane, piperazine, morpholine, quinuclidine, pyrrolidine, azetidine, oxetane, aziridine, dioxane, and pentamethylene sulfide. be done.
• both R 1 and R 2 in the above formula (1-1) have 6 or more carbon atoms which may have a substituent, because the optical properties when made into a film are good. or an optionally substituted cycloalkane ring having 6 or more carbon atoms, such as a cyclohexane ring (e.g., 1,4-cyclohexylene group). is more preferred, and a trans-1,4-cyclohexylene group is even more preferred.
• a cyclohexane ring e.g., 1,4-cyclohexylene group
• substituents which the aromatic hydrocarbon ring described above may have include an alkyl group, an alkoxy group, an aryl group, a halogen atom, an ester group, and a mercapto group.
• the alkyl group is preferably, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or a t-butyl group.
• alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable, and carbon An alkoxy group of number 1 to 4 is more preferred, and a methoxy group or an ethoxy group is particularly preferred.
• aryl group for example, an aryl group having 6 to 15 carbon atoms is preferable, and phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10-dimethoxy An anthryl group is more preferred, and a phenyl group is even more preferred.
• the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Among them, a fluorine atom or a chlorine atom is preferable.
• the ester group includes, for example, a methyl ester group, an ethyl ester group, a propyl ester group, a hexyl ester group, an octyl ester group, a dodecyl ester group, a stearyl ester group, etc. Among them, a methyl ester group or an ethyl ester group. is preferred.
• R 1 and R 2 in the above formula (1-1) include the ring structures shown below among the ring structures exemplified above and combinations of the ring structures and substituents exemplified above. .
• * represents a bonding position in the ring structure shown below.
• R 11 to R 16 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.
• L 1 in the above formula (1-1) is preferably a single bond, or -O-, -CO-O- or -O-CO-, and is preferably a single bond. more preferred.
• n in the above formula (1-1) represents an integer of 0 to 2, preferably 0 or 1, more preferably 1.
• the dicarboxylic acid represented by the above formula (1) is ) is preferably a compound represented by
• p represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0.
• s represents an integer of 1 to 3, preferably 1 or 2, more preferably 2. However, when s represents 2 or 3, multiple p may be the same or different.
• dicarboxylic acid represented by the above formula (1) preferably include compounds represented by the following formula.
• Alcohol derivative used in the production method of the present invention is an alcohol derivative represented by the following formula (2).
• X 1 is a halogen atom, an optionally substituted alkylsulfonyloxy group, an optionally substituted arylsulfonyloxy group, or a substituted represents a heteroarylsulfonyloxy group which may be
• SP 1 is one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms.
• P 1 represents a hydrogen atom or a polymerizable group.
• the halogen atom represented by one aspect of X 1 in the above formula (2) includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. more preferred.
• examples of the alkylsulfonyloxy group represented by one mode of X 1 include a methanesulfonyloxy group.
• examples of the arylsulfonyloxy group represented by one mode of X 1 include a toluenesulfonyloxy group and a benzenesulfonyloxy group.
• examples of the heteroarylsulfonyloxy group represented by one mode of X 1 include a thiophenesulfonyloxy group.
• the alkylsulfonyloxy group and the like, which may be substituted, include the aromatic hydrocarbon rings exemplified as the ring structures in the description of R 1 and R 2 in the above formula (1-1). The same substituents as those which may be possessed may be mentioned.
• X 1 in the above formula (2) is preferably a group represented by the following formula (2-1) for the reason that the selectivity of the dicarboxylic acid monoester is further improved.
• R4 represents an alkyl group, an aryl group or a heteroaryl group which may have a substituent.
• the alkyl group is preferably, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, , isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, methyl group or t- A butyl group is particularly preferred.
• aryl group for example, an aryl group having 6 to 15 carbon atoms is preferable, and phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9, A 10-dimethoxyanthryl group is more preferred, and a phenyl group or a tolyl group is even more preferred.
• heteroaryl group examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, m-carbazolyl, and azepinyl.
• substituents that may be possessed by an alkyl group or the like include the aromatic hydrocarbon rings exemplified as ring structures in the description of R 1 and R 2 in the above formula (1-1). The same substituents as those which may be present may be mentioned.
• the linear or branched alkylene group having 1 to 12 carbon atoms represented by one aspect of SP 1 in the formula (2) includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and hexylene. group, methylhexylene group, heptylene group, and the like.
• one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms are —O—, —S—, —NH—, — N (Q)- or -CO- may be a divalent linking group substituted with -CO-, and the substituent represented by Q includes R 1 and R in the above formula (1-1)
• the same substituents as the substituents that the aromatic hydrocarbon ring exemplified as the ring structure may have may be mentioned.
• the polymerizable group represented by one aspect of P 1 in the formula (2) is not particularly limited, a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
• a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
• the radically polymerizable group a known radically polymerizable group can be used, and acryloyloxy group or methacryloyloxy group can be mentioned as suitable groups.
• an acryloyloxy group is known to generally have a high polymerization rate, and an acryloyloxy group is preferred from the viewpoint of improving productivity, but a methacryloyloxy group can also be used as the polymerizable group.
• the cationically polymerizable group known cationically polymerizable groups can be used. and the like.
• an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group or a vinyloxy group is particularly preferable.
• particularly preferred polymerizable groups include polymerizable groups represented by any of the following formulas (P-1) to (P-20).
• P 1 in the above formula (2) is preferably a polymerizable group, more preferably a polymerizable group represented by the above formula (P-1) or (P-2). preferable.
• the group represented by SP 1 -P 1 preferably includes the groups shown below.
• * represents the bonding position with X1.
• alcohol derivative represented by the above formula (2) include compounds represented by the following formula.
• the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) are reacted using a base in a protic solvent, and the formula (3) described below is obtained. ) or the dicarboxylic acid monoester represented by (4).
• a protic solvent is a solvent that releases protons by dissociation, such as water, alcohols, and fatty acids.
• protic solvents include: water; Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol , isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol , 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-methyl-1-hexanol, 1-nonanol, 3,5,5
• water methanol, ethanol, n-propanol, i-propanol, n-butanol, or tert-butanol is used as the protic solvent for the reason that the selectivity of the dicarboxylic acid monoester is further improved.
• Water is preferred, and water is more preferred.
• other protic solvents such as methanol and ethanol may be used in combination.
• the base is not particularly limited, it is preferably an inorganic base from the viewpoint of solubility in protic solvents.
• inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; substances; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; cesium fluoride;
• Bronsted bases inorganic Bronsted bases are preferred from the viewpoints of solubility in protic solvents, suppression of side reactions, and the like.
• inorganic Bronsted bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as calcium hydroxide and barium hydroxide; hydroxides; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal hydrogen carbonate chloride such as cesium hydrogen carbonate; alkali metal hydrogen phosphate chloride such as disodium hydrogen phosphate and dipotassium hydrogen phosphate; and the like.
• alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide
• alkaline earth metals such as calcium hydroxide and barium hydroxide
• hydroxides alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate
• the above formula (1) it is preferable to form and use an alkali metal salt or an alkaline earth metal salt of the represented dicarboxylic acid. That is, in the present invention, the reaction between the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) is performed by converting the dicarboxylic acid represented by the above formula (1) into a dicarboxylic acid in advance. may be converted into an alkali metal salt or an alkaline earth metal salt, and then reacted with the alcohol derivative represented by the above formula (2).
• reaction conditions of the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) are not particularly limited except that the above-described protic solvent and base are used.
• the reaction conditions for the conversion can be appropriately adopted.
• the reaction temperature is preferably -10 to 150°C, more preferably -5 to 120°C, even more preferably -5 to 100°C.
• the reaction time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 hour to 8 hours.
• the amount of the alcohol derivative represented by the above formula (2) is not particularly limited, but it is 0.8 to 5.0 equivalents with respect to the dicarboxylic acid represented by the above formula (1). , more preferably 1.0 to 4.0 equivalents, even more preferably 1.0 to 3.0 equivalents.
• the amount of the base to be used is not particularly limited, but it is preferably 1.0 to 5.0 equivalents with respect to the dicarboxylic acid represented by the above formula (1), and 1.5 It is more preferably ⁇ 3.0 equivalents, and even more preferably 1.8 to 2.5 equivalents.
• additives include potassium iodide, sodium iodide, tetraalkylammonium salts (eg, tetrabutylammonium chloride, tetrabutylammonium bromide, etc.), crown ethers (eg, 18-crown-6, etc.), and the like. is mentioned.
• a dicarboxylic acid monoester represented by the following formula (3) or (4) is produced by the reaction described above.
• W, SP 1 and P 1 are the same as defined in formulas (1) and (2) above, and their specific examples are also the same.
• M represents an alkali metal atom or an alkaline earth metal atom.
• m represents the valence of M in the above formula (4).
• W, SP 1 and P 1 present in plurality in the above formula (4) may all be the same or different.
• alkali metal atom represented by one aspect of M in the above formula (4) include sodium, potassium, lithium, and cesium, with sodium, potassium, and lithium being preferred.
• alkaline earth metal atom represented by one aspect of M include calcium, strontium, and barium, and among these, calcium and barium are preferable.
• the dicarboxylic acid monoester represented by the above formula (3) or (4) is used for the reason that the film has good optical properties and the selectivity of the dicarboxylic acid monoester is further improved.
• the compound represented by the following formula (3-1) or (4-1) is a compound represented by the above formula (1-1) as the dicarboxylic acid represented by the above formula (1). can be generated by
• R 1 , R 2 , L 1 and n are the same as defined in formula (1-1) above, and specific examples thereof are also the same.
• SP 1 , P 1 , M and m are the same as defined in formulas (3) and (4) above, and the specific examples thereof are also the same.
• the optical properties when made into a film are improved, and the selectivity of the dicarboxylic acid monoester is further improved.
• the compound represented by the following formula (3-2) or (4-2) can be obtained by using the compound represented by the above formula (1-2) as the dicarboxylic acid represented by the above formula (1). can be generated.
• dicarboxylic acid monoesters represented by the above formulas (3), (3-1) and (3-2) include compounds represented by the following formulas.
• dicarboxylic acid monoesters represented by the above formulas (4), (4-1) and (4-2) include compounds represented by the following formulas: are preferably mentioned.
• Ma represents an alkali metal atom.
• the dicarboxylic acid monoester salt of the present invention is a compound represented by the above formula (4-2).
• compound (I-1-a) 10.0 g (39.3 mmol), N,N-dimethylacetamide (DMAc) 100 mL, triethylamine 8.0 mL (78.6 mmol), and 433 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature (23° C.).
• 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the mixture and stirred at 100° C. for 5 hours.
• the ratio of monoester (I-1) and diester (I-1-c) was found to be 40:29 by HPLC analysis, and the monoester selectivity was 58%. .
• 100 mL of 1N hydrochloric acid and 100 mL of ethyl acetate were added, stirred at room temperature (23° C.) for 10 minutes, and filtered.
• the filtrate was separated, the organic layer was washed with 10% saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
• 100 mL of chloroform was added to the residue, the resulting white crystals were filtered, and the filtrate was evaporated under reduced pressure.
• the resulting crude product was purified by silica gel column chromatography to obtain 4.78 g (12.6 mmol) of monoester (I-1) (yield 32%).
• Example 1 suppresses the formation of the diester (I-1-c) more than the synthesis method of Comparative Example 1, and the monoester (I-1) It was found that the selectivity of
• Example 2 A monoester (I-1) was synthesized in the same manner as in Example 1, except that sodium hydroxide was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 3.15 g (78.6 mmol) of sodium hydroxide and 320 mL of water, and the mixture was heated to 60°C. Dissolved. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to this solution and stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of monoester (I-1) and diester (I-1-c) was found to be 35:1.2 by HPLC analysis, and the monoester selectivity was 97%. there were.
• Example 3 A monoester (I-1) was synthesized in the same manner as in Example 1, except that potassium hydroxide was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 4.41 g (78.6 mmol) of potassium hydroxide and 320 mL of water, and the mixture was heated to 60°C. Dissolved. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to this solution and stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found by HPLC analysis to be 21.1:0.8, with a monoester selectivity of 96. %Met.
• Example 4 A monoester (I-1) was synthesized in the same manner as in Example 1, except that sodium hydrogen carbonate was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 4.25 g (78.6 mmol) of sodium hydrogencarbonate and 320 mL of water, and the mixture was heated to 60°C. Dissolved. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to this solution and stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of monoester (I-1) and diester (I-1-c) was found to be 27.1:0.7 by HPLC analysis, and the monoester selectivity was 97. %Met.
• Example 5 In the same manner as in the scheme of Example 1, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 320 mL of water, and the mixture was heated to 60°C. Warm to dissolve. After heating this solution to 80° C., 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added and stirred at 80° C. for 2 hours.

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