Method for producing iodine-containing tertiary alcohol ester

Abstract

Disclosed is a method for producing an iodine-containing tertiary alcohol ester, the method including: a nucleophilic step for reacting an iodine-containing compound represented by formula (1) with a nucleophilic agent; and an acylation step for adding an acylating agent to the reaction liquid obtained in the nucleophilic step so as to obtain an iodine-containing tertiary alcohol ester. The nucleophilic step and the acylation step are continuously performed without having an isolation step after the nucleophilic step.

Description

Method for producing iodine-containing tertiary alcohol esters

[0001] The present invention relates to a novel method for producing an iodine-containing tertiary alcohol ester.

[0002] In recent years, advances in lithography technology have led to rapid advances in miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. A common method for miniaturizing pixels is to shorten the wavelength of the exposure light source. Specifically, while ultraviolet light, typically g-line and i-line, has traditionally been used, far-ultraviolet exposure using KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) has now become the norm for mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also being increasingly adopted. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films. Examples include polymethyl methacrylate, polyhydroxystyrene or polyalkyl methacrylate having an acid-dissociable group (see, for example, Non-Patent Document 1). In recent years, development of iodine-containing polymers that may be useful in lithography processing has been progressing (see, for example, Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2018-172640

[0005] Shinji Okazaki and 8 others, "40 Years of Lithography Technology," S&T Publishing, December 9, 2016

[0006] As described in Patent Document 1, the demand for iodine-containing polymers as resist materials has been increasing in recent years. Iodine-containing polymers can be synthesized using iodine-containing tertiary alcohol esters, etc. Generally, ester compounds are synthesized by reacting a corresponding alcohol with an acylating agent. However, in the case of tertiary alcohol esters, due to the bulkiness of the corresponding tertiary alcohol, it may be difficult to obtain the ester compound from the alcohol compound using the above-mentioned method. Furthermore, the above-mentioned method requires the tertiary alcohol to be separately synthesized and purified, which has disadvantages such as complex work and extended production time.

[0007] In order to solve the above-mentioned problems, an object of the present invention is to provide a method for producing an iodine-containing tertiary alcohol ester, which can synthesize an iodine-containing tertiary alcohol ester with high purity and efficiency.

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by reacting an iodine-containing compound having a specific structure in a specific step, and have thus completed the present invention. That is, the present invention is as follows.

[0009] <1> A method for producing an iodine-containing tertiary alcohol ester, comprising: a nucleophilic step of reacting an iodine-containing compound represented by the following formula (1) with a nucleophilic agent; and an acylation step of adding an acylating agent to a reaction solution obtained in the nucleophilic step to obtain an iodine-containing tertiary alcohol ester, wherein the nucleophilic step and the acylation step are carried out consecutively without an isolation step after the nucleophilic step: (Wherein, A represents an aromatic ring having 6 to 12 carbon atoms, and —R １ is -O-R ２ (R ２ represents an alkyl group or an aryl group), —X (X represents F, Cl, Br or I), —O—CO—R ４ (R ４ is an alkyl group, an aryl group, or R １ represents a moiety other than —CO—), —NR ５ R ６ (R ５ , R ６R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ may be bonded to form a ring structure.) or —OH, I is an iodine atom, Y is a monovalent substituent having 0 to 30 carbon atoms, n is an integer of 1 or 2, m is an integer of 1 or greater, k is 0 or an integer of 1 or greater, and the total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring.) <2> The method for producing an iodine-containing tertiary alcohol ester according to <1> above, wherein the nucleophilic step and the acylation step are carried out in the same reaction vessel. <3> The method for producing an iodine-containing tertiary alcohol ester according to <1> or <2> above, wherein the step is carried out under light-blocking conditions. <4> The method for producing an iodine-containing tertiary alcohol ester according to any one of <1> to <3> above, wherein the nucleophile is a nucleophile other than an organolithium reagent. <5> The method for producing an iodine-containing tertiary alcohol ester according to any one of <1> to <4> above, wherein a nucleophilic catalyst is used in the acylation step. <6> The method for producing an iodine-containing tertiary alcohol ester according to any one of <1> to <5>, further comprising a step of adding silica gel and removing impurities. <7> The method for producing an iodine-containing tertiary alcohol ester according to any one of <1> to <6>, further comprising a step of adding silica gel and removing impurities. <8> The method for producing an iodine-containing tertiary alcohol ester according to any one of <1> to <6>, further comprising a step of adding silica gel and removing impurities.

[0010] According to the present invention, it is possible to provide a method for producing an iodine-containing tertiary alcohol ester, which can synthesize an iodine-containing tertiary alcohol ester with high purity and efficiency.

[0011] Hereinafter, an embodiment of the present invention will be described (hereinafter, may be referred to as "the present embodiment"). Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only the present embodiment.

[0012] In this specification, when a numerical range is expressed using "-" as "X to Y", the range includes the extreme values ​​X and Y.

[0013] <<Method for Producing Iodine-Containing Tertiary Alcohol Ester>> The method for producing an iodine-containing tertiary alcohol ester of this embodiment (hereinafter sometimes simply referred to as the "production method of this embodiment") includes a nucleophilic step of reacting an iodine-containing compound represented by formula (1) described below (hereinafter sometimes referred to as the "raw iodine compound") with a nucleophile, and an acylation step of adding an acylating agent to the reaction solution obtained in the nucleophilic step to obtain an iodine-containing tertiary alcohol ester, and the nucleophilic step and the acylation step are performed consecutively without an isolation step after the nucleophilic step. Examples of compounds obtained by the reaction of the iodine-containing compound with the nucleophile in the nucleophilic step include iodine-containing tertiary alkoxides (hereinafter sometimes referred to as "tertiary alkoxides").

[0014] (Wherein, A represents an aromatic ring having 6 to 12 carbon atoms, and —R １ is -O-R ２ (R ２ represents an alkyl group or an aryl group), —X (X represents F, Cl, Br or I), —O—CO—R ４ (R ４ is an alkyl group, an aryl group, or R １ represents a moiety other than —CO—), —NR ５ R ６ (R ５ , R ６ R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ may be bonded to form a ring structure; or -OH, I is an iodine atom, Y is a monovalent substituent having 0 to 30 carbon atoms, n is an integer of 1 or 2, m is an integer of 1 or greater, k is 0 or an integer of 1 or greater, and the total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring.

[0015] A typical method for synthesizing an iodine-containing tertiary alcohol ester involves reacting an iodine-containing compound with a nucleophilic agent (nucleophilic step), followed by reacting the resulting compound with an acylating agent (acylation step) to synthesize the desired iodine-containing tertiary alcohol ester. However, if a large amount of impurities is generated in the nucleophilic step, in order to increase the yield, it is desirable to remove the impurities by quenching the activated compound produced in the nucleophilic reaction to form an iodine-containing tertiary alcohol, which is then isolated and purified. However, using the isolated iodine-containing tertiary alcohol can make it difficult to esterify the alcohol in the acylation step. While the reason for this is unclear, it is speculated that one factor is that the bulky molecular structure of iodine-containing tertiary alcohols inhibits their reaction with acylating agents such as acid anhydrides due to steric hindrance.

[0016] In contrast, the production method of the present embodiment involves reacting a nucleophilic agent with an iodine-containing compound represented by formula (1) to generate a corresponding tertiary alkoxide, which is then reacted with an acylating agent without quenching or isolating the alkoxide, thereby obtaining an iodine-containing tertiary alcohol ester. The production method of the present embodiment uses an iodine-containing compound represented by formula (1) having a moiety represented by -(C=O)-R (where R is an atom other than carbon) as a raw material, resulting in less impurities being generated than when an iodine-containing ketone compound or the like is used as a raw material. Therefore, it is not necessary to quench the activated form (tertiary alkoxide) generated by the nucleophilic reaction after the nucleophilic step and isolate it as an iodine-containing tertiary alcohol. Furthermore, the production method of the present embodiment involves consecutively performing the nucleophilic step and the acylation step without an isolation step after the nucleophilic step, thereby enabling the synthesis of an iodine-containing tertiary alcohol ester from the raw material iodine-containing compound represented by formula (1) without the intervention of an iodine-containing tertiary alcohol. Therefore, according to the production method of this embodiment, it is possible to easily and efficiently obtain an iodine-containing tertiary alcohol ester with high purity. The production method of this embodiment will be described in detail below.

[0017] <Nucleophilic Step> In the present embodiment, the nucleophilic step is a step of reacting an iodine-containing compound (raw iodine compound) represented by formula (1) with a nucleophilic agent. The reaction of the raw iodine compound with the nucleophilic agent can produce an activated iodine-containing tertiary alkoxide (tertiary alkoxide).

[0018] (Iodine-containing compound represented by formula (1)) The iodine-containing compound (starting iodine compound) used in the nucleophilic step is a compound represented by formula (1). As described above, the starting iodine compound is a compound having a moiety represented by -(C=O)-R (R is an atom other than carbon).

[0019]

[0020] In formula (1), A represents an aromatic ring having 6 to 12 carbon atoms; １ is -O-R ２ (R ２ represents an alkyl group or an aryl group), —X (X represents F, Cl, Br or I), —O—CO—R ４ (R ４ is an alkyl group, an aryl group, or R １ represents a moiety other than —CO—), —NR ５ R ６ (R ５ , R ６ R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ may be bonded to form a ring structure. ) or -OH, I is an iodine atom, Y is a monovalent substituent having 0 to 30 carbon atoms, n is an integer of 1 to 2, m is an integer of 1 or more, k is 0 or an integer of 1 or more, and the total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring. When k and n are each 2 or more, each R １ , Y may be the same or different.

[0021] In formula (1), A represents an aromatic ring having 6 to 12 carbon atoms. Examples of the aromatic ring include benzene, naphthalene, and biphenol, with a benzene ring and a naphthalene ring being preferred, and a benzene ring being more preferred.

[0022] In formula (1), R １ is -O-R ２ (R ２ represents an alkyl group or an aryl group), —X (X represents F, Cl, Br or I), —O—CO—R ４ (R ４ is an alkyl group, an aryl group, or R １ represents a moiety other than —CO—), —NR ５ R ６ (R ５ , R ６ R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ may be bonded to form a ring structure.) or represents —OH. In formula (1), n ​​represents an integer of 1 to 2, and is preferably 1 in terms of reactivity and the like.

[0023] -O-R ２ R forms an ester group in combination with the -(C=O)- moiety in formula (1). ２ represents an alkyl group or an aryl group. ２ Examples of the alkyl group and aryl group represented by the formula (I) are not particularly limited, but include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, icosyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, adamantyl, ethylene, propylene, butylene, phenyl, naphthyl, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, benzopyrene, azulene, and fluorene groups, which may contain an ether bond, a ketone bond, or an ester bond.

[0024] The groups exemplified above include isomers, for example, a propyl group includes an n-propyl group and an isopropyl group, and a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

[0025] The above-mentioned R ２ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. ２ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. ２ The alkyl group or aryl group represented by the formula (I) is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group or an ethyl group. ２ may be the same or different.

[0026] -X, in combination with the -(C=O)- moiety in formula (1), constitutes an acid halide group. X represents F, Cl, Br, or I, with Cl, F, and Br being preferred, Cl and F being more preferred, and Cl being particularly preferred. When n is 2 or greater, each X may be the same or different.

[0027] -O-CO-R ４ R forms an acid anhydride group in combination with the —(C═O)— moiety in formula (1). ４ is an alkyl group, an aryl group, or R １ Indicates a moiety other than —CO—. ４ Examples of the alkyl group and aryl group represented by the formula ２ Examples of alkyl groups and aryl groups are given above. ４ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. ４ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. ４The alkyl group or aryl group represented by the formula (I) is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, more preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group or an ethyl group. ４ may be the same or different.

[0028] R ４ is R in formula (1) １ When a moiety other than —CO— is shown, the starting iodine compound has a dimer structure as shown in the following formula (1-1).

[0029]

[0030] In formula (1-1), A, R １ , I, Y, m, and k are the same as in formula (1). Each o independently represents 0 or 1. The total number of o, m, and k does not exceed the number of groups that can be bonded to the aromatic ring. When o and k are each 1 or more, each R １ , Y may be the same or different.

[0031] -NR ５ R ６ R forms an amide group in combination with the —(C═O)— moiety in formula (1). ５ , R ６ R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ Examples of the alkyl group and aryl group represented by the formula ２ Examples of alkyl groups and aryl groups are given for R ５ , R ６ Examples of the alkoxy group represented by the formula (I) include groups in which an oxygen atom is bonded to these alkyl or aryl groups. ５ , R ６ The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. ５ , R ６The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 16 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. ５ , R ６ The alkoxy group represented by the formula (I) is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 7 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. ５ , R ６ In terms of reactivity, at least one of the groups is preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 7 carbon atoms.

[0032] Also, R ５ , R ６ may be bonded to form a ring structure. Such a ring structure may contain oxygen atoms, sulfur atoms, nitrogen atoms, etc. in addition to carbon atoms. ５ R ６ In this case, R ５ , R ６ Examples of the ring structure to which the group is bonded include morpholine, pyrrole, and benzotriazole structures.

[0033]

[0034] The above-mentioned R ５ , R ６ As a combination of ５ : methyl group, ethyl group, propyl group, butyl group, benzyl group, R ６ A combination of a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is preferred, and R ５ : methyl group, ethyl group, benzyl group, R ６ R is more preferably a methoxy group, an ethoxy group, or a propoxy group, ５ : methyl group, ethyl group, R ６ Particularly preferred are a methoxy group and an ethoxy group. When n is 2 or more, each R ５ , R ６ may be the same or different.

[0035] The —OH group, in combination with the —(C═O)— moiety in formula (1), constitutes an acid group (—COOH).

[0036] As described above, in the production method of this embodiment, in formula (1), "-(C=O)-R １ " corresponds to any one of an ester group, an acid halide group, an acid anhydride group, an amide group, and a carboxylic acid group, and among these, "-(C=O)-R １ The group represented by " is preferably an ester group or an acid halide group, and particularly preferably an ester group.

[0037] In formula (1), "I" is an iodine atom, and m is an integer of 1 or greater. From the viewpoint of sensitization effect, m is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.

[0038] In formula (1), "Y" represents a monovalent substituent having 0 to 30 carbon atoms. Examples of the substituent include an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group or hydroxyalkyl group having 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than iodine, a formyl group, a nitro group, an amino group, a thiol group, or a hydroxyl group. Among these groups, those that can have a substituent may further have a substituent. As the monovalent substituent having 0 to 30 carbon atoms represented by Y, from the viewpoints of polarity adjustment and sensitization effect, a hydroxyl group, an alkoxy group, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, or a halogen atom other than iodine is preferred, a hydroxyl group, an alkoxy group, an alkyl group, an alkenyl group, an alkynyl group, or a halogen atom other than iodine is more preferred, and a hydroxyl group, an alkoxy group, an alkyl group, an alkenyl group, an alkynyl group, or a halogen atom other than iodine is particularly preferred. Examples of Y other than alkoxy groups such as hydroxyl, methoxy and ethoxy include -OMOM (methoxymethoxy), -OEM (ethoxymethoxy), -OTHP (tetrahydro-2H-pyran-2-yloxy), -OEE (1-ethoxyethoxy), etc., in which the -OH group is protected. In addition, in formula (1), k represents an integer of 0 or 1 or more, and is preferably 0 to 2 from the viewpoint of reactivity.

[0039] Specific examples of iodine-containing compounds represented by formula (1) are shown below. However, the iodine-containing compounds represented by formula (1) are not limited to the following specific examples. In the following chemical formulae, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, "Bu" represents a butyl group, "Ac" represents an acetyl group, "THP" represents a tetrahydropyranyl group, "EE" represents an ethoxyethyl group, and "EM" represents an ethoxymethyl group. Furthermore, notations such as "NMeOMe" mean an amide group in which -Me (methyl group) and -OMe (methoxy group) are bonded to N (nitrogen atom), respectively.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] The iodine-containing compound represented by formula (1) in this embodiment can be synthesized by a known method, including, but not limited to, a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like, a method of reacting iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943), or a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (e.g., JP 63-101342 A, JP 2003-64012 A).

[0046] (Nucleophile) In the nucleophilic step, the raw material iodine compound represented by formula (1) is reacted with a nucleophile. With ordinary iodine-containing compounds, a metal-halogen exchange reaction with the nucleophile generally proceeds, resulting in decomposition of the substrate. In particular, when an organolithium reagent is used as the nucleophile, the metal-halogen exchange reaction is likely to proceed. For this reason, it is preferable to use a nucleophile other than an organolithium reagent as the nucleophile, and it is even more preferable not to use an organolithium reagent as the nucleophile. The nucleophile other than the organolithium reagent is not particularly limited, but an organomagnesium reagent or an organocerium reagent is preferred, with an organomagnesium reagent being particularly preferred. For example, it is preferable to use a magnesium-containing Grignard reagent. Examples of Grignard reagents include methylmagnesium bromide, ethylmagnesium bromide, and the like.

[0047] In the nucleophilic step, the nucleophilic agent is preferably used in an amount of 2 equivalents or more relative to the starting iodine compound in the present embodiment, more preferably 2.5 equivalents or more in order to efficiently consume the starting iodine compound, and particularly preferably 2.5 to 6 equivalents.

[0048] (Conditions for Nucleophilic Step, etc.) In the nucleophilic step, the reaction temperature between the raw material iodine compound and the nucleophile is preferably from room temperature to 110°C, more preferably from 30°C to 110°C, and particularly preferably from 30°C to 66°C, in order to improve reactivity.

[0049] In the nucleophilic step, the reaction time is not particularly limited, and the preferred range varies depending on the selection of raw materials and the desired yield. From the viewpoint of suppressing impurities, the reaction time is preferably 0.1 to 48 hours, more preferably 0.1 to 24 hours, and particularly preferably 0.1 to 12 hours.

[0050] In the nucleophilic step, in addition to the raw material iodine compound and the nucleophilic agent, a solvent and a known additive used in the nucleophilic reaction of an ester, an acid halide, an acid anhydride, an amide, or an acid can be used as necessary. An example of the known additive is cerium chloride.

[0051] The solvent is not particularly limited, and any solvent that can be used in the nucleophilic reaction of the starting iodine compound can be used. For example, a wide variety of reaction solvents can be used, including polar aprotic solvents, protic polar solvents, and non-polar aprotic solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and non-polar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A reaction solvent is effective but not essential.

[0052] From the viewpoint of being used continuously in the acylation reaction, preferred solvents include THF (tetrahydrofuran), cyclopentyl methyl ether, 2-methyltetrahydrofuran, diethyl ether, and toluene, and THF is more preferred. The amount of solvent used in the nucleophilic reaction is not particularly limited, but from the viewpoint of reactivity and solubility, it can be, for example, preferably 280 to 4200 parts by mass, more preferably 280 to 1700 parts by mass, and particularly preferably 320 to 1700 parts by mass relative to 100 parts by mass of the iodine raw material.

[0053] <One-pot process> In the production method of this embodiment, the nucleophilic step and the acylation step are carried out consecutively without an isolation step after the nucleophilic step. Here, the "isolation step" refers to a step of isolating the compound produced in the nucleophilic step after the nucleophilic step and before the acylation step. Here, the compound produced in the nucleophilic step includes an iodine-containing tertiary alkoxide (tertiary alkoxide) represented by the following formula (2). The following tertiary alkoxide is an activated form corresponding to the raw material iodine compound.

[0054] (In formula (2), A, I, Y, n, m, and k are the same as in formula (1). Rx and Ry each independently represent a monovalent substituent derived from a nucleophile. The total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring represented by A. When n and k are 2 or more, each Y, Rx, and Ry may be the same or different.)

[0055] In formula (2), Rx and Ry each independently represent a monovalent substituent derived from a nucleophile. Examples of the monovalent substituent include a methyl group, an ethyl group, a propyl group, and a butyl group. Specific examples of Rx and Ry include a methyl group, an ethyl group, a propyl group, and a butyl group for both Rx and Ry.

[0056] Furthermore, in the production method of this embodiment, the nucleophilic step and the acylation step may be carried out continuously using the same reaction vessel, or different reaction vessels may be used for the nucleophilic step and the acylation step. However, from the viewpoint of efficiency, it is preferable to carry out the nucleophilic step and the acylation step in the same reaction vessel.

[0057] <Acylation Step> The acylation step in this embodiment is a step of adding an acylating agent to the reaction solution obtained in the nucleophilic step to obtain the target iodine-containing tertiary alcohol ester. In the production method of this embodiment, the activated form (tertiary alkoxide) obtained in the nucleophilic step is quenched to isolate the iodine-containing tertiary alcohol, and the alcohol is not used in the acylation step. Instead, the tertiary alkoxide can be reacted directly with the acylating agent without being converted into a tertiary alcohol. Therefore, a highly pure and efficient iodine-containing tertiary alcohol ester can be obtained.

[0058] The obtained iodine-containing tertiary alcohol ester includes an iodine-containing tertiary alcohol ester represented by the following formula (3).

[0059] (In formula (3), A, I, Y, n, m, k, Rx, and Ry are the same as those in formula (2). The total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring represented by A. When n and k are 2 or more, each Y, Rx, and Ry may be the same or different.)

[0060] The acylating agent is not particularly limited as long as it is a compound that can be used in the acylation reaction of tertiary alkoxides, but from the viewpoint of reactivity, acid anhydrides and acid halides are preferred, and acid anhydrides are more preferred. Examples of acid anhydrides include methacrylic acid anhydride, acrylic acid anhydride, acetic anhydride, etc., and from the viewpoint of the intended use of the product, methacrylic acid anhydride and acrylic acid anhydride are preferred. Furthermore, examples of acid halides include methacrylic acid chloride, acrylic acid chloride, acetyl chloride, etc., and from the viewpoint of the intended use of the product, methacrylic acid chloride and acrylic acid chloride are preferred.

[0061] In the acylation step, the acylating agent is preferably used in an amount of 2 equivalents or more relative to the starting iodine compound in the present embodiment in terms of reactivity, and in order to efficiently consume the tertiary alkoxide, the acylating agent is more preferably used in an amount of 2.5 equivalents or more, and particularly preferably used in an amount of 2.5 to 7.0 equivalents.

[0062] (Nucleophilic Catalyst) In the production method of this embodiment, it is preferable to use a nucleophilic catalyst to improve the reactivity of the acylating agent. The nucleophilic catalyst is not particularly limited as long as it is a nucleophilic catalyst that can be used in the acylation reaction of a tertiary alkoxide. For example, from the viewpoint of activating the acylating agent, 4-dimethylaminopyridine (DMAP), 4-pyrrolidinopyridine (PPY), 9-azajulolidine, and 1,4-diazabicyclo[2.2.2]octane (DABCO) are preferred, and 4-dimethylaminopyridine (DMAP) is more preferred.

[0063] In the acylation step, in order to efficiently proceed with the reaction, the nucleophilic catalyst is preferably used in an amount of 0.01 to 1.0 equivalent relative to the iodine raw material, and in order to efficiently consume the tertiary alkoxide, it is more preferable to use 0.01 to 0.5 equivalents or more, and particularly preferably 0.01 to 0.1 equivalents.

[0064] (Conditions for Acylation Step, etc.) In the acylation, the reaction temperature when the acylating agent is added to the reaction solution obtained in the nucleophilic step is preferably −20 to 50° C., more preferably −10 to 40° C., and particularly preferably 0 to 30° C., in order to improve reactivity.

[0065] In the acylation, the reaction time is not particularly limited, and the preferred range varies depending on the selection of the acylating agent and the nucleophilic catalyst and the desired yield. The reaction time is preferably 0.1 to 48 hours, more preferably 0.1 to 24 hours, and particularly preferably 0.1 to 12 hours, in terms of efficient consumption of the tertiary alkoxide.

[0066] In the acylation step, in addition to the acylating agent and the nucleophilic catalyst, a solvent, a known additive used in the acylation reaction of a tertiary alkoxide, etc. may be used as needed. Examples of known additives include Bi(OTf) ３ , Sc(OTf) ３ , ZnCl ２ The solvent is not particularly limited, and any solvent that can be used in the acylation reaction of a tertiary alkoxide can be used; however, from the viewpoint of using the solvent used in the nucleophilic step as is, THF (tetrahydrofuran), cyclopentyl methyl ether, 2-methyltetrahydrofuran, diethyl ether, and toluene are preferred, and THF is more preferred. The amount of reaction solvent used in the acylation step is not particularly limited, and the solvent used in the nucleophilic step can be used as is, but the amount of solvent may be appropriately adjusted so that, for example, it is preferably 280 to 4200 parts by mass, more preferably 280 to 1700 parts by mass, and particularly preferably 320 to 1700 parts by mass per 100 parts by mass of the iodine raw material or tertiary alkoxide (preferably, the raw material iodine compound).

[0067] The iodine-containing tertiary alcohol ester obtained by the reaction can be isolated and purified as a desired high-purity monomer by known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon separation and purification, or a combination thereof. The purification step will be described later.

[0068] (Light-shielding conditions) Iodine-containing compounds and compounds having a polymerizable group may be decomposed or polymerized by light, resulting in a decrease in purity. Therefore, in the production method of this embodiment, it is preferable to carry out the reaction under light-shielding conditions in order to improve the purity of the iodine-containing tertiary alcohol ester. In other words, it is preferable that the production method of this embodiment is carried out under light-shielding conditions. Specifically, it is preferable that at least one of the nucleophilic step and the acylation step in this embodiment is carried out under light-shielding conditions, and it is more preferable that at least both the nucleophilic step and the acylation step are carried out under light-shielding conditions.

[0069] Here, "conducting under light-shielded conditions" means conducting under an environment where light with a wavelength of 500 nm or less is dimmed, such as under a yellow lamp. Although not particularly limited, the nucleophilic step and the acylation step are conducted under conditions where the irradiation intensity of light with a wavelength of 500 nm or less is 10 mW / m ２ It is preferable that the following is carried out:

[0070] (Other Steps) The production method of the present embodiment may include other steps in addition to the nucleophilic step and the acylation step. Examples of the other steps include a purification step, an adsorption step, and a polymerization inhibitor addition step.

[0071] Purification Process—The purification process applicable to the manufacturing method of this embodiment is not particularly limited, but may be the method described in International Publication No. 2015 / 080240 or International Publication No. 2018 / 159707. Specifically, this purification method includes the steps of dissolving the compound in an organic solvent that is immiscible with water to obtain an organic layer, contacting the organic layer with an acidic aqueous solution to perform an extraction process, thereby transferring metals contained in the organic layer (organic phase) containing the compound and the organic solvent to an aqueous layer (aqueous phase), and then separating the organic layer from the aqueous layer. The organic solvent that is immiscible with water is typically an organic solvent classified as a water-insoluble solvent. The organic solvent is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of organic solvent used is typically about 10% by mass relative to the compound used.

[0072] Specific examples of the organic solvent to be used include those described in WO 2015 / 080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc. are preferred, and toluene, cyclohexanone, and propylene glycol monomethyl ether acetate are particularly preferred.

[0073] The acidic aqueous solution can be appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include those described in International Publication No. 2015 / 080240. These acidic aqueous solutions can be used alone or in combination of two or more. Examples of the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. The pH range of the acidic aqueous solution is approximately 0 to 5, and more preferably approximately 0 to 3.

[0074] - Adsorption Step - Generally, compounds having a polymerizable group may produce impurities such as polymers, resulting in a decrease in purity. For this reason, the production method of this embodiment may include a step (adsorption step) of adding and dispersing an adsorbent after the reaction to remove impurities in the reaction solution obtained through the nucleophilic step and the acylation step.

[0075] The adsorbent is not particularly limited, but examples thereof include silica gel, modified silica gel, activated carbon, activated alumina, zeolite, hydrotalcite, florisil, activated clay, diatomaceous earth, synthetic adsorbents, ion exchange resins, etc. Modified silica gel includes sulfuric acid-supported silica gel, etc. Among these, from the viewpoint of effectively adsorbing polar groups contained in high-molecular-weight impurities, silica gel, zeolite, activated alumina, ion exchange resins, and modified silica gel are preferred, silica gel, modified silica gel, and ion exchange resins are more preferred, and silica gel is even more preferred. In other words, the production method of this embodiment can include a step of adding silica gel to the reaction solution and removing impurities.

[0076] Examples of methods for using the adsorbent include a method in which the adsorbent is added to the reaction liquid obtained through the nucleophilic step and the acylation step, followed by stirring, and then filtering off the adsorbent, and a method in which the reaction liquid obtained through the nucleophilic step and the acylation step is passed through a container, column, filter, etc. filled with the adsorbent. From the viewpoint of production, the method in which the adsorbent is added to the reaction liquid and stirred is preferred.

[0077] The amount of adsorbent used is not particularly limited and can be appropriately set depending on the adsorbent used, the iodine-containing tertiary alcohol ester, the solvent, the temperature, the desired yield, etc. From the viewpoint of achieving high purity, the amount of adsorbent used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 0.3 to 20 parts by mass, per part by mass of the iodine-containing tertiary alcohol ester of the target compound.

[0078] In the adsorption step, the temperature is not particularly limited, and the preferred range varies depending on the adsorbent, the concentration of the target iodine-containing tertiary alcohol ester, the content of high-molecular-weight impurities, etc., but from the viewpoint of adsorption, the temperature is preferably −80° C. or higher and 80° C. or lower, more preferably −50° C. or higher and 60° C. or lower, even more preferably −30° C. or higher and 50° C. or lower, and particularly preferably −20° C. or higher and 30° C. When silica gel is used as the adsorbent, the temperature range is preferably −80° C. or higher and 80° C. or lower.

[0079] -Polymerization Inhibitor- In the production method of this embodiment, it is preferable to add a polymerization inhibitor in the acylation step, the purification step, or the adsorption step.

[0080] As the polymerization inhibitor, a commercially available product that is generally available can be used. For example, nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole; N,N'-diphenyl-p-phenylenediamine; N-phenyl-N'-isopropylamine; Examples of the polymerization inhibitor include amines such as isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether, phenols such as p-methoxyphenol (also known as methoquinone), 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexane oxime and p-quinone dioxime, and dialkylthiodipropionates. The amount of the polymerization inhibitor added is, for example, 0.001 to 10 parts by mass, and preferably 0.01 to 1 part by mass, per 100 parts by mass of the iodine-containing tertiary alcohol ester.

[0081] [Film-Forming Composition] The iodine-containing tertiary alcohol ester obtained by the production method of this embodiment can be used in various applications, for example, in a film-forming composition. The film-forming composition may be, for example, a lithography film-forming composition that can be used for forming a film for semiconductor lithography. The film-forming composition may also be a resist film-forming composition that can be used for forming a resist film (i.e., a "resist composition"). Furthermore, the film-forming composition can be used for forming an upper layer film (i.e., an "upper layer film-forming composition"), an intermediate layer (i.e., an "intermediate layer-forming composition"), an underlayer film (i.e., an "underlayer film-forming composition"), etc. These compositions can primarily or supplementarily perform optical or electromagnetic radiation functions such as anti-reflection and secondary electron diffusion prevention, and pattern quality improvement functions such as preventing pattern collapse and defects due to chemical and physical effects and maintaining pattern shape, for the purpose of improving the patterning performance of the resist layer in the lithography process. The composition of this embodiment can form a film with high sensitivity and can also provide a good resist pattern shape.

[0082] The film-forming composition containing the iodine-containing tertiary alcohol ester obtained by the production method of this embodiment can also be used as an optical component-forming composition applying lithography technology. Optical components are used in film and sheet form, and are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as a filling film and planarizing film on photodiodes, planarizing films before and after color filters, microlenses, and planarizing and conformal films on microlenses, which are components of solid-state imaging elements that require a high refractive index.

[0083] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0084] [Measurement Method] [LC (Liquid Chromatography) Measurement Conditions] LC in each example was measured as follows: Apparatus name: Shimadzu Corporation (Nexera-i LC-2020C 3D) Column: Waters XBridge BEH C18 (2.5 μm 3.0 × 75 mm) Detector: PDA; flow rate: 0.7 mL / min, column oven temperature: 40°C, autosampler temperature: 15°C, input volume: 1.0 μL (2 mg / mL THF solution) Eluent (%): ultrapure water: MeCN: 1% phosphoric acid aqueous solution (0:98:2) to (93:5:2)

[0085] [GPC measurement conditions] Device name: Shimadzu Corporation (Nexera-i LC-2020C 3D) Column: ACQUITY APC XT45 (molecular weight cutoff range 200-5000) Detector: PDA; flow rate: 0.3 mL / min, column temperature: 30°C, autosampler temperature: 15°C, calibration curve: none, injection volume 1.0 μL (2 mg / mL THF solution) Eluent: THF for LC

[0086] [Compound Structure] The compound structure was determined using a Bruker Avance 500III spectrometer under the following conditions: １ The product was confirmed by H-NMR measurement. Frequency: 500 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: TMS Measurement temperature: 23 ° C. Also, １３ C-NMR measurement was carried out using the same apparatus under the following conditions: Frequency: 125 MHz Solvent: CDCl ３ , or d ６ -DMSO internal standard: solvent used

[0087] [Example 1]

[0088] (Nucleophilic Step) Under light-shielding conditions (an environment in which light with a wavelength of 500 nm or less was reduced under a yellow lamp (trade name: fluorescent lamp with anti-scattering film for semiconductor factories, pure yellow (FLR40SYFMP), manufactured by Panasonic Corporation; the same applies hereinafter)), a 200 mL three-neck flask was prepared, and 38 mL of dehydrated THF and 5.0 g (19.1 mmol) of methyl 4-iodobenzoate (a raw material iodine compound purchased from Tokyo Chemical Industry Co., Ltd.) were added, followed by N ２ The mixture was stirred for 30 minutes under a flow rate while cooling with ice so that the internal temperature was kept below 10° C. After 57 mL (57 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 200 mL three-neck flask over 5 minutes, the internal temperature was returned to 25° C. over 15 minutes, and then the internal temperature was raised to 50° C. over 20 minutes, and stirring was continued for 40 minutes.

[0089] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), the mixture was ice-cooled to an internal temperature of 10°C or less, and then 10.3 g (66.8 mmol) of methacrylic anhydride (acylating agent) was added dropwise over 5 minutes. Thereafter, 0.23 g (1.91 mmol) of DMAP (nucleophilic catalyst) was added all at once, and the internal temperature was returned to 25°C over 20 minutes, after which stirring was continued for 3 hours. After ice-cooling to an internal temperature of 10°C or less, 15 g of saturated aqueous ammonium chloride solution was added dropwise over 5 minutes. Next, 45 g of ion-exchanged water was added dropwise over 10 minutes, and then 300 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Further, 60 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by distillation under reduced pressure while blowing in a small amount of air until no solvent components were distilled out, thereby obtaining a crude product. The resulting crude product was purified using a silica gel column to obtain the target iodine-containing tertiary alcohol ester (1) (4.7 g, 14.2 mmol). 1 mg of methoquinone was added as a polymerization inhibitor to the resulting iodine-containing tertiary alcohol ester.

[0090] As a result of analysis, the LC purity at 220 nm of the obtained crude product was 87% and the GPC purity was 88%, and the LC purity at 220 nm of the iodine-containing tertiary alcohol ester obtained after column purification was 99% and the GPC purity was 99%.

[0091] The resulting compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, confirming that the compound had the chemical structure of the iodine-containing tertiary alcohol ester compound (1). δ (ppm) (d-DMSO): 7.68 (2H, Ph), 7.16 (2H, Ph), 6.03 (1H, ═CH ２ ), 5.66 (1H, =CH ２ ), 1.85 (3H, -CH ３ ), 1.71 (6H, -CH ３ )

[0092] [Example 2]

[0093] (Nucleophilic Step) Under a light-shielded condition, a 200 mL three-necked flask was prepared, and 38 mL of dehydrated THF and 5.1 g (19.1 mmol) of 4-iodobenzoyl chloride (a raw material iodine compound; purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto. ２ The mixture was stirred for 30 minutes under a flow of water while being cooled with ice so that the internal temperature was kept at 10° C. or lower. 57 mL (57 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 200 mL three-neck flask over 5 minutes, and then the mixture was stirred for 40 minutes under ice cooling so that the internal temperature was kept at 10° C. or lower.

[0094] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), 10.3 g (66.8 mmol) of methacrylic anhydride (acylating agent) was added dropwise over 5 minutes. Thereafter, 0.23 g (1.91 mmol) of DMAP (nucleophilic catalyst) was added all at once, and the internal temperature was returned to 25 ° C. over 20 minutes, followed by continued stirring for 3 hours. After ice cooling to an internal temperature of 10 ° C. or less, 15 g of saturated aqueous ammonium chloride solution was added dropwise over 5 minutes. Next, 45 g of ion-exchanged water was added dropwise over 10 minutes, and then 300 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Further, 60 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by distillation under reduced pressure while blowing in a small amount of air until no solvent components were distilled out, thereby obtaining a crude product. The crude product was purified using a silica gel column to obtain the target iodine-containing tertiary alcohol ester (4.5 g, 13.6 mmol). 1 mg of methoquinone was added as a polymerization inhibitor to the resulting iodine-containing tertiary alcohol ester.

[0095] As a result of analysis, the LC purity at 220 nm of the obtained crude product was 85% and the GPC purity was 86%, and the LC purity at 220 nm of the iodine-containing tertiary alcohol ester obtained after column purification was 97% and the GPC purity was 98%.

[0096] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0097] [Example 3] An iodine-containing tertiary alcohol ester was obtained in the same manner as in Example 1, except that the light-shielding conditions were not used (the reaction was carried out under normal fluorescent light). Column purification using silica gel afforded the tertiary alcohol ester (4.4 g, 13.3 mmol).

[0098] As a result of analysis, the LC purity at 220 nm of the obtained crude product was 80% and the GPC purity was 83%, and the LC purity at 220 nm of the iodine-containing tertiary alcohol ester obtained after column purification was 96% and the GPC purity was 97%.

[0099] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0100] [Example 4]

[0101] (Nucleophilic Step) Under a light-shielded condition, a 100 mL three-neck flask was prepared, and 10 mL of dehydrated THF and 0.5 g (1.91 mmol) of methyl 4-iodobenzoate (a raw material iodine compound; purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto. ２ The mixture was stirred for 15 minutes under a flow of water while cooling so that the internal temperature was −70° C. or lower. 3.0 mL (4.2 mmol, 1.4 M cyclopentyl methyl ether solution) of methyllithium (nucleophile: organolithium reagent) was added to a 100 mL three-neck flask over 5 minutes, and the mixture was stirred for 15 minutes.

[0102] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), 1.03 g (6.68 mmol) of methacrylic anhydride (acylating agent) was added dropwise over 1 minute. Thereafter, 0.023 g (0.19 mmol) of DMAP (nucleophilic catalyst) was added all at once, and the internal temperature was returned to 25 ° C. over 10 minutes, followed by continued stirring for 3 hours. After ice cooling to an internal temperature of 10 ° C. or less, 5 g of saturated aqueous ammonium chloride solution was added dropwise over 1 minute. Next, 15 g of ion-exchanged water was added dropwise over 2 minutes, and then 100 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Further, 30 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by distillation under reduced pressure while blowing in a small amount of air until no solvent components were distilled out, thereby obtaining a crude product. The resulting crude product was purified using a silica gel column to obtain the target iodine-containing tertiary alcohol ester (0.013 g, 0.0394 mmol, 2% yield). 1 mg of methoquinone was added to the resulting iodine-containing tertiary alcohol ester as a polymerization inhibitor. The LC purity at 220 nm of the resulting compound was 95%, and the GPC purity was 96%.

[0103] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0104] [Example 5]

[0105] (Nucleophilic Step) Under a light-shielded condition, a 200 mL three-necked flask was prepared, and 38 mL of dehydrated THF and 5.0 g (19.1 mmol) of methyl 4-iodobenzoate (a raw material iodine compound purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto. ２ The mixture was stirred for 30 minutes under a flow rate while cooling with ice so that the internal temperature was kept below 10° C. After 57 mL (57 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 200 mL three-neck flask over 5 minutes, the internal temperature was returned to 25° C. over 15 minutes, and then the internal temperature was increased to 50° C. over 20 minutes, and stirring was continued for 40 minutes.

[0106] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), the mixture was ice-cooled to an internal temperature of 10°C or less, and then 110.3 g (66.8 mmol) of methacrylic anhydride (acylating agent) was added dropwise over 5 minutes. Thereafter, the internal temperature was returned to 25°C over 20 minutes, and stirring was continued for 3 hours. After ice-cooling to an internal temperature of 10°C or less, 15 g of saturated aqueous ammonium chloride solution was added dropwise over 5 minutes. Next, 45 g of ion-exchanged water was added dropwise over 10 minutes, and then 300 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Further, 60 g of ion-exchanged water was added, stirred for 15 minutes, allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by distillation under reduced pressure while blowing in a small amount of air until no solvent components were distilled out, thereby obtaining a crude product. Analysis of the crude product showed that the LC purity at 220 nm was 62%, with 25% of the tertiary alcohol remaining unreacted.

[0107] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0108] [Example 6]

[0109] (Nucleophilic Step) Under a light-shielded condition, a 200 mL three-necked flask was prepared, and 38 mL of dehydrated THF and 5.0 g (19.1 mmol) of methyl 4-iodobenzoate (a raw material iodine compound purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto. ２ The mixture was stirred for 30 minutes under a flow rate while cooling with ice so that the internal temperature was kept below 10° C. After 57 mL (57 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 200 mL three-neck flask over 5 minutes, the internal temperature was returned to 25° C. over 15 minutes, and then the internal temperature was increased to 50° C. over 20 minutes, and stirring was continued for 40 minutes.

[0110] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), the mixture was ice-cooled to an internal temperature of 10 ° C. or less, and then 10.3 g (66.8 mmol) of methacrylic anhydride (acylating agent) was added dropwise over 5 minutes. Then, 0.23 g (1.91 mmol) of DMAP (nucleophilic catalyst) was added all at once, and the internal temperature was returned to 25 ° C. over 20 minutes, and stirring was continued for 3 hours. After ice-cooling to an internal temperature of 10 ° C. or less, 15 g of saturated aqueous ammonium chloride solution was added dropwise over 5 minutes. Next, 45 g of ion-exchanged water was added dropwise over 10 minutes, and then 300 g of toluene was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. Further, 60 g of ion-exchanged water was added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. This operation was repeated twice. The recovered organic layer was concentrated by vacuum distillation while blowing in a small amount of air until no solvent components were distilled out, and then 5.0 g of silica gel was dispersed at 25°C and filtered to obtain the target iodine-containing tertiary alcohol ester (4.9 g, 14.8 mmol). The LC purity at 220 nm of the obtained tertiary alcohol ester was 90%, and the GPC purity was 91%.

[0111] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0112] Example 7 In the experiment of Example 6, when dispersion treatment with silica gel was not performed, the LC purity at 220 nm measured without column purification was 87%, and the GPC purity was 88%.

[0113] The obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, and the same peaks as in Example 1 were found, confirming that the compound had the chemical structure of iodine-containing tertiary alcohol ester compound (1).

[0114] Comparative Example 1 (Synthesis and methacrylation of tertiary alcohol)

[0115] (Nucleophilic Step) Under a light-shielded condition, a 100 mL three-necked flask was prepared, and 25 mL of dehydrated THF and 1.23 g (5.0 mmol) of 4-iodoacetophenone were added thereto. ２ The mixture was stirred for 30 minutes under ice cooling to keep the internal temperature at 10°C or below under a flow rate. 6.0 mL (6.0 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 100 mL three-necked flask over 5 minutes, followed by stirring for 1 hour. 10 g of saturated aqueous ammonium chloride solution was then added dropwise over 5 minutes, and 50 g of ethyl acetate was added. After stirring for 15 minutes and allowing to stand, the aqueous layer was drained. 50 g of saturated saline was then added, stirred for 15 minutes, and allowed to stand, allowing the aqueous layer to be drained. The recovered organic layer was concentrated by distillation under reduced pressure until no solvent components were distilled out, and the target tertiary alcohol (0.82 g, 3.1 mmol) was isolated by column purification using silica gel.

[0116] (Acylation Step) Under a light-shielded condition, a 100 mL three-necked flask was prepared, and 13 mL of dehydrated THF and 1.0 g (3.8 mmol) of the tertiary alcohol obtained by the above-mentioned method were added thereto. ２ The mixture was stirred for 30 minutes under a flow rate while being cooled to an internal temperature of 10°C or less. 0.74g (5.7mmol) of N,N-diisopropylethylamine (DIPEA) was added to a 100mL three-neck flask at once, followed by 0.05g (0.41mmol) of DMAP (nucleophilic catalyst). 0.48g (4.6mmol) of methacrylic acid chloride (acylating agent) was then added dropwise at once. The internal temperature was returned to 25°C over 10 minutes, and stirring was continued for 3 hours or more. The reaction was monitored using TLC, but the reaction did not proceed at all, and the target product could not be obtained.

[0117] [Example 8] (Synthesis using ethyl ester raw material) Synthesis of 2-(4-iodophenyl)propan-2-yl methacrylate

[0118] ​(Nucleophilic Step) Under a light-shielded condition, a 500 mL three-necked flask was prepared, and 36 mL of dehydrated THF and 10.0 g (36.2 mmol) of ethyl 4-iodobenzoate (a raw material iodine compound purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto. ２ The mixture was stirred for 30 minutes under a flow rate while being cooled with ice so that the internal temperature was kept below 10° C. After 91 mL (91 mmol, 1.0 M THF solution) of methylmagnesium bromide (nucleophile: Grignard reagent) was added to a 500 mL three-neck flask over 40 minutes, the internal temperature was returned to 25° C. over 15 minutes, and then the internal temperature was increased to 50° C. over 20 minutes, and stirring was continued for 120 minutes.

[0119] (Acylation step) Subsequently (without isolating the compound produced in the nucleophilic step), the mixture was ice-cooled to an internal temperature of 10 ° C. or less, and 0.44 g (3.6 mmol) of DMAP (nucleophilic catalyst) was added all at once, followed by dropwise addition of 16.2 g (105 mmol) of methacrylic anhydride (acylating agent) over 5 minutes. Thereafter, the internal temperature was returned to 25 ° C. over 20 minutes, and stirring was continued for 1 hour. After ice-cooling to an internal temperature of 10 ° C. or less, 91 g of a 20% aqueous ammonium chloride solution was added dropwise over 20 minutes, and the mixture was stirred overnight and allowed to stand, after which the aqueous layer was drained. An additional 52 g of toluene was added, and 40 g of 5% sodium bicarbonate water was added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. This operation was repeated three times. Furthermore, 40 g of ion-exchanged water was added, stirred for 15 minutes, and then allowed to stand, and the aqueous layer was drained. This operation was repeated three times. The collected organic layer was concentrated by vacuum distillation while blowing in a small amount of air until no solvent components were distilled out, yielding a crude product. The crude product was purified using a silica gel column to obtain the target iodine-containing tertiary alcohol ester (10.2 g, 30.8 mmol). 1 mg of methoquinone was added to the resulting iodine-containing tertiary alcohol ester as a polymerization inhibitor.

[0120] (Analysis Results) As a result of analysis, the crude product obtained had an LC purity of 90% at 220 nm and a GPC purity of 92%, while the iodine-containing tertiary alcohol ester obtained after column purification had an LC purity of 99% at 220 nm and a GPC purity of 99%. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, confirming that it had the chemical structure of the above-mentioned iodine-containing tertiary alcohol ester compound (2-(4-iodophenyl)propan-2-yl methacrylate). δ (ppm) (d-DMSO): 7.68 (2H, Ph), 7.16 (2H, Ph), 6.03 (1H, ═CH ２ ), 5.66 (1H, =CH ２ ), 1.85 (3H, -CH ３ ), 1.71 (6H, -CH ３ )

[0121] Example 9: Synthesis of 2-(3-iodophenyl)propan-2-yl methacrylate 2-(3-Iodophenyl)propan-2-yl methacrylate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl methacrylate described in Example 8, except that 9.5 g (36.2 mmol) of methyl 3-iodobenzoate (raw material iodine compound; purchased from Sigma-Aldrich) was used instead of ethyl 4-iodobenzoate.

[0122] (Analysis Results) As a result of analysis, the LC purity at 220 nm of the obtained crude product was 88%, the GPC purity was 90%, and the iodine-containing tertiary alcohol ester obtained after column purification had an LC purity at 220 nm of 99% and a GPC purity of 99%. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the above-mentioned iodine-containing tertiary alcohol ester compound (2-(3-iodophenyl)propan-2-yl methacrylate). δ (ppm) (d-DMSO): 7.69 (1H, Ph), 7.62 (1H, Ph), 7.32 (1H, Ph), 7.12 (1H, Ph), 6.04 (1H, =CH ２ ), 5.67 (1H, =CH２ ), 1.83 (3H, -CH ３ ), 1.69 (6H, -CH ３ )

[0123] [Example 10] Synthesis of 2-(2-iodophenyl)propan-2-yl methacrylate

[0124] 2-(2-Iodophenyl)propan-2-yl methacrylate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl methacrylate described in Example 8, except that 9.5 g (36.2 mmol) of methyl 2-iodobenzoate (raw material iodine compound; purchased from Sigma-Aldrich) was used instead of ethyl 4-iodobenzoate.

[0125] (Analysis Results) As a result of analysis, the LC purity at 220 nm of the obtained crude product was 91%, the GPC purity was 92%, and the iodine-containing tertiary alcohol ester obtained after column purification had an LC purity at 220 nm of 99% and a GPC purity of 99%. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the above-mentioned iodine-containing tertiary alcohol ester compound (2-(2-iodophenyl)propan-2-yl methacrylate). δ (ppm) (d-DMSO): 7.94 (1H, Ph), 7.62 (1H, Ph), 7.32 (1H, Ph), 6.93 (1H, Ph), 6.05 (1H, =CH ２ ), 5.68 (1H, =CH ２ ), 1.81 (3H, -CH ３ ), 1.73 (6H, -CH ３ )

[0126] Example 11: Synthesis of 2-(3-iodo-4-methoxyphenyl)propan-2-yl methacrylate

[0127] ​​2-(3-Iodo-4-methoxyphenyl)propan-2-yl methacrylate was obtained in the same manner as in the synthesis of 2-(4-iodophenyl)propan-2-yl methacrylate described in Example 8, except that 10.6 g (36.2 mmol) of methyl 3-iodo-4-methoxybenzoate (raw material iodine compound; purchased from Tokyo Chemical Industry Co., Ltd.) was used instead of ethyl 4-iodobenzoate.

[0128] (Analysis Results) As a result of analysis, the LC purity at 220 nm of the obtained crude product was 89%, the GPC purity was 90%, and the iodine-containing tertiary alcohol ester obtained after column purification had an LC purity at 220 nm of 99% and a GPC purity of 99%. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the above-mentioned iodine-containing tertiary alcohol ester compound (2-(3-iodo-4-methoxyphenyl)propan-2-yl methacrylate). δ (ppm) (d-DMSO): 7.79 (1H, Ph), 7.38 (1H, Ph), 6.80 (1H, Ph), 6.02 (1H, ═CH ２ ), 5.66 (1H, =CH2), 3.88 (3H, O-CH ３ ), 1.80 (3H, -CH ３ ), 1.69 (6H, -CH ３ )

[0129] The disclosure of Japanese Patent Application No. 2024-030044, filed on February 29, 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards mentioned in the specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing an iodine-containing tertiary alcohol ester, comprising: a nucleophilic step of reacting an iodine-containing compound represented by the following formula (1) with a nucleophilic agent; and an acylation step of adding an acylating agent to the reaction solution obtained in the nucleophilic step to obtain an iodine-containing tertiary alcohol ester, wherein the nucleophilic step and the acylation step are carried out consecutively without an isolation step after the nucleophilic step. (Wherein, A represents an aromatic ring having 6 to 12 carbon atoms, and —R １ is -O-R ２ (R ２ represents an alkyl group or an aryl group), —X (X represents F, Cl, Br or I), —O—CO—R ４ (R ４ is an alkyl group, an aryl group, or R １ represents a moiety other than —CO—), —NR ５ R ６ (R ５ , R ６ R each independently represents a hydrogen atom, an alkoxy group, an alkyl group, or an aryl group. ５ , R ６ may be bonded to form a ring structure; or -OH, I is an iodine atom, Y is a monovalent substituent having 0 to 30 carbon atoms, n is an integer of 1 or 2, m is an integer of 1 or greater, k is 0 or an integer of 1 or greater, and the total number of n, m, and k does not exceed the number of groups that can be bonded to the aromatic ring.

2. The method for producing an iodine-containing tertiary alcohol ester according to claim 1, wherein the nucleophilic step and the acylation step are carried out in the same reaction vessel.

3. The method for producing an iodine-containing tertiary alcohol ester according to claim 1, which is carried out under light-shielded conditions.

4. The method for producing an iodine-containing tertiary alcohol ester according to claim 1, wherein the nucleophile is a nucleophile other than an organolithium reagent.

5. The method for producing an iodine-containing tertiary alcohol ester according to claim 1, wherein a nucleophilic catalyst is used in the acylation step.

6. The method for producing the iodine-containing tertiary alcohol ester according to claim 1, further comprising the step of adding silica gel to remove impurities.

7. The method for producing an iodine-containing tertiary alcohol ester according to claim 1, wherein the compound obtained by the reaction of the iodine-containing compound with the nucleophilic agent in the nucleophilic step includes an iodine-containing tertiary alkoxide.

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