WO2013141064A1 - Procédé de production de (méth)acrylate d'adamantyle - Google Patents

Procédé de production de (méth)acrylate d'adamantyle Download PDF

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Publication number
WO2013141064A1
WO2013141064A1 PCT/JP2013/056688 JP2013056688W WO2013141064A1 WO 2013141064 A1 WO2013141064 A1 WO 2013141064A1 JP 2013056688 W JP2013056688 W JP 2013056688W WO 2013141064 A1 WO2013141064 A1 WO 2013141064A1
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Prior art keywords
meth
adamantyl
acrylate
reaction
general formula
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PCT/JP2013/056688
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English (en)
Japanese (ja)
Inventor
田中　慎司
義崇 上野山
直弥 河野
大野　英俊
小島　明雄
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出光興産株式会社
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Publication of WO2013141064A1 publication Critical patent/WO2013141064A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a method for producing adamantyl (meth) acrylate, and more particularly to a method for efficiently producing adamantyl (meth) acrylates useful as a photoresist raw material.
  • Adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, is a highly symmetric and stable compound, and its derivative exhibits a unique function. Etc. are known to be useful.
  • adamantyl (meth) acrylate has recently attracted attention as a monomer for a resin for a photoresist by utilizing its acid sensitivity, dry etching resistance, ultraviolet ray transparency, and the like.
  • adamantyl (meth) acrylate for example, tertiary alcohol such as 1- (1-adamantyl) -1-methylethanol, adamantane carboxylic acid alkyl ester or adamantane carboxylic acid halide, organometallic compound and (meta ) It is carried out by a method of esterification by reacting with an acrylic acid halide (for example, see Patent Documents 1 and 2).
  • an object of the present invention is to provide a method for efficiently producing adamantyl (meth) acrylate suitable as a monomer for a photoresist resin with high purity.
  • this invention provides the manufacturing method of the adamantyl (meth) acrylate represented by the following general formula (i) which makes a metal alkoxide and a (meth) acrylic anhydride react.
  • each R 1 independently represents an alkyl group having 1 to 3 carbon atoms, and R 3 represents a hydrogen atom or a methyl group.
  • a method for efficiently producing adamantyl (meth) acrylate suitable as a monomer for a photoresist resin with high purity is provided.
  • the method for producing adamantyl (meth) acrylate of the present invention is a method for producing adamantyl (meth) acrylate represented by the following general formula (i).
  • R 1 is an alkyl group having 1 to 3 carbon atoms.
  • R 3 is a hydrogen atom or a methyl group.
  • the alkyl group having 1 to 3 carbon atoms may be linear or branched, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • Examples of the adamantyl (meth) acrylate represented by the general formula (i) include 1- (1-adamantyl) -1-methylethyl (meth) acrylate and 1- (1-adamantyl) -1-ethylpropyl (meth). Acrylate, 1- (1-adamantyl) -1-propylbutyl (meth) acrylate, 1- (1-adamantyl) -1-isopropyl-2-methylpropyl (meth) acrylate, etc. (1-adamantyl) -1-methylethyl (meth) acrylate and 1- (1-adamantyl) -1-ethylpropyl (meth) acrylate are preferred.
  • reaction formula in the method for producing adamantyl (meth) acrylate of the present invention is specifically represented by the following formula.
  • R 1 and R 3 are the same as described above.
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • X 1 represents a halogen atom.
  • the general formula (5) is a metal alkoxide, which is a reaction intermediate formed by the reaction of 1-adamantanecarboxylic acid ester with an organometallic compound.
  • the 1-adamantyl alkyl alcohol represented by the general formula (6) is a byproduct (unreacted product) in the reaction between the metal alkoxide (reaction intermediate) and (meth) acrylic anhydride.
  • a 1-adamantanecarboxylic acid ester represented by the general formula (1) is reacted with a metal organic compound represented by the following general formula (2) or (3). It is preferable to carry out by reacting (meth) acrylic anhydride with the metal alkoxide (reaction intermediate) represented by the general formula (5). These reactions are usually preferably carried out in an organic solvent.
  • the 1-adamantylalkyl alcohol represented by the general formula (6) and an organic lithium compound such as alkyllithium, an alkali metal such as sodium metal or lithium metal, or a Grignard reagent are used.
  • (Meth) acrylic anhydride is used as an esterifying agent in the present invention.
  • the (meth) acrylic anhydride acrylic anhydride, methacrylic anhydride, or a mixed acid anhydride thereof can be used.
  • the amount of (meth) acrylic anhydride used is usually 1 to 6 moles, more preferably 1 to 5 moles, and more preferably 1 to 4 moles per mole of metal alkoxide. Further preferred.
  • the amount of (meth) acrylic anhydride to be used with respect to 1 mol of the carboxylic acid ester represented by the general formula (1) is usually preferably 1 to 6 mol from the viewpoint of efficiently obtaining the desired product.
  • the amount is more preferably 1 to 5 mol, and further preferably 1 to 4 mol.
  • the 1-adamantanecarboxylic acid ester used in the present invention is represented by the following general formula (1).
  • R 2 represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group having 1 to 3 carbon atoms may be either linear or branched. Specifically, methyl Group, ethyl group, n-propyl group and isopropyl group.
  • Examples of the 1-adamantane carboxylate represented by the general formula (1) include methyl 1-adamantanecarboxylate, ethyl 1-adamantanecarboxylate, n-propyl 1-adamantanecarboxylate, and isopropyl 1-adamantanecarboxylate. From the viewpoint of reactivity, methyl 1-adamantanecarboxylate is preferable.
  • the 1-adamantanecarboxylic acid ester represented by the general formula (1) can be obtained by a usual esterification reaction between an adamantylcarboxylic acid and an alcohol in the presence of an acid catalyst.
  • the organometallic compound used in the present invention is represented by the following general formula (2) or (3).
  • X 1 represents a halogen atom.
  • the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • Representative examples of the organometallic compounds represented by the general formulas (2) and (3) include organomagnesium compounds such as methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride (Grignard reagent etc.); methyllithium, ethyl And organic lithium compounds such as lithium and isopropyl lithium.
  • the organomagnesium compound can also be used in combination with a copper halide.
  • methyl magnesium chloride, ethyl magnesium chloride, methyl lithium, and ethyl lithium are preferable.
  • the amount of the organometallic compound to be used is generally 2 to 6 mol, preferably 2 to 4 mol, more preferably 2 to 3 mol, per 1 mol of the carboxylic acid ester represented by the general formula (1).
  • organic solvent examples include hydrocarbon solvents such as n-hexane and n-heptane, and ether solvents such as diethyl ether and tetrahydrofuran. Of these, toluene and tetrahydrofuran are preferred. When tetrahydrofuran is used, since the effect of stabilizing the reaction intermediate is high, the target product can be obtained in high yield.
  • these solvents may be used alone or in a combination of two or more.
  • the said solvent may be mixed with respect to the metal alkoxide represented by the said General formula (5), and this invention may be implemented by one continuous reaction.
  • the reaction temperature can be appropriately selected depending on the type of reaction components, but is usually preferably in the range of ⁇ 20 to 100 ° C. From the viewpoint of not reducing the reaction rate and suppressing polymerization of the (meth) acryloyl group, a range of 0 to 50 ° C. is preferable.
  • the reaction pressure is usually preferably in the range of 0.01 to 0.1 MPa in absolute pressure. If it is this range, a special pressure
  • In the reaction of 1-adamantanecarboxylic acid ester with a metal organic compound, and the reaction of a reaction intermediate obtained by the above reaction with (meth) acrylic anhydride usually 1 minute to 24 hours, preferably 30 minutes to The range is 5 hours.
  • the salt is removed by washing with water, followed by washing with a basic aqueous solution.
  • a basic aqueous solution examples include inorganic basic compounds such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and ammonia, and organic basic compounds such as ethylenediamine, aniline, triethylamine and pyridine. It is done.
  • distillation, crystallization, column separation, etc. are possible and can be selected depending on the properties of the product and the type of impurities, but recrystallization or crystallization using water and a water-soluble solvent is particularly used.
  • the desired adamantyl (meth) acrylate can be produced with high purity and high yield. Specifically, after distilling off the solvent from the post-treated reaction solution, water and a water-soluble solvent are added, and if necessary, high purity adamantyl (meth) acrylate is precipitated by cooling. Let The precipitate can be separated by a method such as filtration or centrifugation.
  • water-soluble solvents examples include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and glycerin, ether solvents such as tetrahydrofuran and dioxane, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, and acetone. Of these, methanol is preferred.
  • GC gas chromatography
  • LC liquid chromatography
  • GC-MS gas chromatography mass spectrometry
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared spectroscopy
  • Example 1 (Synthesis process) To 40 g (206 mmol) of methyl 1-adamantanecarboxylate obtained in Production Example 1, 40 g of toluene was added to replace with nitrogen, followed by cooling with a refrigerant. While maintaining this toluene solution at 10 ° C. or lower, 247 g (494 mmol) of a THF solution of methylmagnesium chloride (2M) was added dropwise over 4.5 hours, and then the temperature was naturally raised to 3 at room temperature (25 ° C.). Time reaction was performed.
  • Example 2 to 6 The reaction was carried out in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1 to obtain 1- (1-adamantyl) -1-methylethyl methacrylate, respectively.
  • Table 1 shows the reaction conditions and GC analysis results.
  • Example 7 To 126 g (650 mmol) of methyl 1-adamantanecarboxylate obtained in Production Example 1, 1.5 L of THF was added and dissolved, and the atmosphere was replaced with nitrogen. Next, 26 g (3770 mol) of lithium is added, and 146 mL (1960 mol) of ethyl bromide is dropped over 2 hours while maintaining at 10 ° C. or less by cooling with a refrigerant, whereby ethyl lithium is formed. Thereafter, the reaction was carried out for 15 hours while the temperature was naturally raised.
  • the mixture was cooled again with a refrigerant, and 101 g (660 mmol) of methacrylic anhydride was added dropwise over about 10 minutes while maintaining the temperature at 10 ° C. or lower. Then, it was made to react for 3 hours, raising temperature naturally. After removing residual lithium from the crude reaction solution by decantation, the reaction was stopped by adding 300 mL of water while maintaining the temperature at 25 ° C. or lower. The aqueous layer was separated, extracted with hexane, washed with saturated brine, and dried over magnesium sulfate.
  • the solution was filtered and concentrated to obtain 140 g of the target 1- (1-adamantyl) -1-ethylpropyl methacrylate (isolation yield: 74%, GC purity: 98.7%).
  • the substrate of the raw material 1 is “methyl 1-adamantanecarboxylate”, and the solvent of the raw material 1 is “toluene (Example 1)” or “THF (tetrahydrofuran) (Examples 2 to 7)”. is there.
  • the substrate of the raw material 2 is “methyl magnesium chloride (Examples 1 to 6)” or “ethyllithium (Example 7)”, and the temperature 2 is “the temperature (° C.) of the reaction solution after the dropwise addition of the raw material 2”. And time 2 indicates “reaction time (h) from the end of dropping of raw material 2”.
  • the raw material 3 is “methacrylic anhydride”, the temperature 3 indicates “temperature of the reaction solution after completion of dropping of the raw material 3 (° C.)”, and the time 3 is “reaction time from the end of dropping of the raw material 3” (H) ".
  • the “residual raw material” in Table 1 refers to an alcohol (compound represented by the general formula (6)) obtained by decomposing the compound represented by the general formula (5) with water.
  • magnesium was decomposed with an aqueous hydrochloric acid solution, and the aqueous layer was separated. Subsequently, the mixture was washed with 10% aqueous sodium hydroxide solution and saturated brine, and concentrated. The concentrated liquid was crystallized from methanol to obtain 37 g of the target 1- (1-adamantyl) -1-methylethanol. The isolation yield was 92% by mass, and the purity measured by GC was 99.1% by mass.
  • Comparative Example 3 In Comparative Example 1, reaction and sampling were performed in the same manner as in Comparative Example 1 except that 0.12 mL (1.5 mmol) of pyridine was used instead of 0.21 mL (1.5 mmol) of triethylamine. Even in the sample, only the peak of 1- (1-adamantyl) -1-methylethanol, which is a raw material, is observed, the target peak of 1- (1-adamantyl) -1-methylethyl methacrylate is not observed, and the reaction is completely I found out that it was not progressing.
  • Comparative Example 4 In Comparative Example 2, reaction and sampling were performed in the same manner as in Comparative Example 2 except that 0.12 mL (1.5 mmol) of pyridine was used instead of 0.21 mL (1.5 mmol) of triethylamine. Only the peak of 1- (1-adamantyl) -1-methylethanol, which is the raw material, is observed, the target peak of 1- (1-adamantyl) -1-methylethyl methacrylate is not observed, and the reaction proceeds at all. I found out.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production efficace d'un (méth)acrylate d'adamantyle d'une grande pureté pouvant être utilisé en tant que monomère pour résine photosensible. L'invention concerne, donc, un procédé de production de (méth)acrylate d'adamantyle représenté par la formule générale (i), procédé dans le cadre duquel un alcoxyde métallique est amené à réagir avec un anhydride (méth)acrylique.
PCT/JP2013/056688 2012-03-23 2013-03-11 Procédé de production de (méth)acrylate d'adamantyle WO2013141064A1 (fr)

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JP2012-067395 2012-03-23
JP2012067395A JP5993171B2 (ja) 2012-03-23 2012-03-23 アダマンチル（メタ）アクリレートの製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113880713A (zh) * 2021-10-15 2022-01-04 江苏汉拓光学材料有限公司 一种光刻胶树脂单体的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6154737B2 (ja) * 2013-12-03 2017-06-28 大阪有機化学工業株式会社 環状脂肪族アクリレート類の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002161070A (ja) * 2000-11-24 2002-06-04 Daicel Chem Ind Ltd 第３級アルコールエステルの製造法
JP2003055301A (ja) * 2001-06-07 2003-02-26 Tokuyama Corp ２−アルキル−２−アダマンチル（メタ）アクリレートの製造方法
LV13006B (en) * 2001-09-28 2003-08-20 Olaines Kimiski Farmaceitiska Method for preparation tert-alkylhydroxyadamantane esters of acrylic or methacrylic acid
JP2010150222A (ja) * 2008-12-26 2010-07-08 Mitsubishi Gas Chemical Co Inc アダマンタチル（メタ）アクリレート類の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002161070A (ja) * 2000-11-24 2002-06-04 Daicel Chem Ind Ltd 第３級アルコールエステルの製造法
JP2003055301A (ja) * 2001-06-07 2003-02-26 Tokuyama Corp ２−アルキル−２−アダマンチル（メタ）アクリレートの製造方法
LV13006B (en) * 2001-09-28 2003-08-20 Olaines Kimiski Farmaceitiska Method for preparation tert-alkylhydroxyadamantane esters of acrylic or methacrylic acid
JP2010150222A (ja) * 2008-12-26 2010-07-08 Mitsubishi Gas Chemical Co Inc アダマンタチル（メタ）アクリレート類の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113880713A (zh) * 2021-10-15 2022-01-04 江苏汉拓光学材料有限公司 一种光刻胶树脂单体的制备方法

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TW201400448A (zh) 2014-01-01
TWI576337B (zh) 2017-04-01
JP2013199440A (ja) 2013-10-03

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