Classifications

• • 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
  • 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
  • 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. It is known to be useful as a raw material for the above.
• adamantyl (meth) acrylate has attracted attention in recent years as a monomer for a resin for a photoresist by utilizing its acid sensitivity, dry etching resistance, ultraviolet ray transmittance, 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).
• Patent Documents 1 and 2 are not satisfactory in yield of the target adamantyl (meth) acrylate, and development of a method for efficiently producing at higher yield is desired. .
• the present invention has been made under such circumstances, and 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 in a high yield. is there.
• R 2 represents an alkyl group having 1 to 3 carbon atoms.
• the (meth) acrylic anhydride is reacted.
• R 3 is a hydrogen atom or a methyl group.
• R 1 is the same as described above.
• [2] The process for producing adamantyl (meth) acrylate according to [1] above, wherein 1-adamantanecarboxylic acid ester is distilled.
• [3] The following general formula (5)
• R 5 is a hydrogen atom or a methyl group.
• R 4 is the same as described above.
• a method for efficiently producing adamantyl (meth) acrylate suitable as a monomer for a photoresist resin in a high yield is provided.
• the method for producing adamantyl (meth) acrylate of the present invention is represented by the method for producing adamantyl (meth) acrylate represented by the following general formula (4) (hereinafter referred to as the present invention 1) and the following general formula (8). It consists of either aspect of the method (henceforth this invention 2) which manufactures adamantyl (meth) acrylate.
• the present invention 1 the method for producing adamantyl (meth) acrylate represented by the following general formula (4) (hereinafter referred to as the present invention 1) and the following general formula (8). It consists of either aspect of the method (henceforth this invention 2) which manufactures adamantyl (meth) acrylate.
• (meth) acrylate” means both acrylate and methacrylate. The same applies to other similar terms.
• R 1 is an alkyl group having 1 to 3 carbon atoms.
• R 3 is a hydrogen atom or a methyl group.
• R 4 is an alkyl group having 1 to 3 carbon atoms or a cyanoalkyl group having 2 to 4 carbon atoms.
• R 5 is a hydrogen atom or a methyl group.
• the alkyl group having 1 to 3 carbon atoms in R 1 and R 4 may be either linear or branched, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. .
• Examples of the cyanoalkyl group having 2 to 4 carbon atoms in R 4 include a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, and the like.
• Examples of the adamantyl (meth) acrylate represented by the general formula (4) 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 and the like.
• 1- (1-adamantyl) -1-methylethyl (meth) acrylate and 1- (1-adamantyl) -1-ethylpropyl (meth) acrylate are preferred.
• Examples of the adamantyl (meth) acrylate represented by the general formula (8) include 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl ( And meth) acrylate and 2-isopropyl-2-adamantyl (meth) acrylate.
• 2-methyl-2-adamantyl (meth) acrylate 2-ethyl-2-adamantyl (meth) acrylate, and 2-isopropyl-2-adamantyl (meth) acrylate are preferred.
• R 1 to R 3 and X 1 are the same as described above.
• the metal alkoxide represented by the general formula (9) is a reaction intermediate produced by the reaction of 1-adamantanecarboxylic acid ester with an organometallic compound.
• the 1-adamantyl alkyl alcohol represented by the general formula (10) is a byproduct (unreacted product) in the reaction between the reaction intermediate and (meth) acrylic anhydride.
• the adamantyl (meth) acrylate represented by the general formula (4) can also be produced by reacting the (meth) acrylic anhydride with the 1-adamantyl alkyl alcohol represented by the general formula (10). .
• the 1-adamantanecarboxylic acid ester represented by the general formula (1) is reacted with the metal organic compound represented by the general formula (2) or (3), and then produced. It is carried out by reacting (meth) acrylic anhydride after adding the carboxylic acid ester compound to the reaction mixture containing the reaction intermediate represented by the general formula (9). These reactions are usually carried out in an organic solvent.
• the present invention 1 is characterized in that a (meth) acrylic anhydride is reacted after adding a carboxylic acid ester compound to a reaction mixture containing the reaction intermediate represented by the general formula (9).
• the excess organometallic compound can be deactivated, so that the production of 1-adamantyl alkyl alcohol represented by the general formula (10) as a by-product is prevented. It can suppress, improve the selectivity of a target object, and can obtain a target object with a high yield.
• 1-adamantanecarboxylic acid ester used in the present invention 1 is represented by the following general formula (1).
• R 2 represents an alkyl group having 1 to 3 carbon atoms, and examples thereof are the same as those described for R 1 and R 4 .
• 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 1-adamantanecarboxylic acid ester used as a raw material it is preferable to use a distilled one.
• the 1-adamantane carboxylic acid ester represented by the general formula (1) may contain impurities derived from 1-adamantane carboxylic acid, which is an equipment for its production process and its production raw material. Therefore, by distilling the 1-adamantanecarboxylic acid ester before subjecting it to the reaction with the organometallic compound, the metal component contained as an impurity can be removed. As a result, the metal impurity content of the obtained adamantyl (meth) acrylate can be reduced, and a highly pure adamantyl (meth) acrylate can be obtained.
• the distilled 1-adamantane carboxylic acid ester for example, a product obtained by purifying the product synthesized by the above esterification reaction by distillation or a product obtained by purifying a commercially available 1-adamantane carboxylic acid ester by distillation may be used. it can.
• the distillation method may be atmospheric distillation or vacuum distillation, but vacuum distillation is preferred from the viewpoint of preventing thermal decomposition and the like.
• the vacuum distillation can be performed by a general method such as simple distillation, rectification, or molecular distillation.
• the distillation temperature depends on the boiling point of the compound to be distilled, it is usually 20 to 180 ° C., preferably 30 to 150 ° C.
• the distillation pressure is preferably 0.1 to 10 mmHg (0.013 to 1.33 kPa), more preferably 0.2 to 5 mmHg (0.027 to 0.667 kPa).
• the distillation method may be batch or continuous.
• the organometallic compound used in the present invention 1 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.
• R 1 is the same as described above.
• organometallic compounds represented by the general formulas (2) and (3) include organomagnesium compounds such as methylmagnesium chloride, ethylmagnesium chloride, n-propylmagnesium chloride, isopropylmagnesium chloride (Grignard reagent, etc.) ); Organic lithium compounds such as methyllithium, ethyllithium, n-propyllithium and isopropyllithium. Among these, methyl magnesium chloride, ethyl magnesium chloride, methyl lithium, and ethyl lithium are preferable.
• the organomagnesium compound can also be used in combination with a copper halide.
• 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).
• carboxylic acid ester compound examples include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, and 3-methoxy acetate.
• Acetic esters such as butyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate; ethyl propionate, n-butyl propionate, isoamyl propionate, etc.
• Phenyl acetate ester such as methyl phenylacetate and phenylethyl acetate
• Benzoate ester such as methyl benzoate and ethyl benzoate, and methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-p Pills, and (meth) etc. (meth) acrylic acid esters of isopropyl acrylate.
• methyl acetate, ethyl acetate, ethyl propionate, ethyl phenylacetate, methyl benzoate, and methyl methacrylate are preferred, and ethyl acetate is more preferred from the viewpoint of persistence in the reaction product.
• carboxylic acid ester compounds may be used alone or in combination of two or more.
• the use amount of the carboxylic acid ester compound is from the number of moles of the organometallic compound represented by the general formula (2) or (3) from the viewpoint of suppressing the production of by-products and improving the selectivity of the target product.
• the range of 0.1 to 5.0 times moles is preferable with respect to the number of moles obtained by subtracting the number of moles equivalent to 2 times the 1-adamantylcarboxylic acid ester represented by the general formula (1), A range of ⁇ 1.5 times mol is more preferable.
• a method for adding the carboxylic acid ester compound in the case of a liquid, it can be directly introduced into the reactor by a syringe or a liquid feed pump. In the case of a solid, there is no problem as long as it can be directly added to the reactor in a powder or granule state.
• 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 preferable, and tetrahydrofuran is more preferable. 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 combination of two or more.
• (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 about 1 to 5 moles with respect to 1 mole of the carboxylic acid ester represented by the general formula (1).
• the reaction temperature in the present invention 1 can be appropriately selected depending on the kind of reaction components, but is preferably in the range of ⁇ 200 to 200 ° C. If the reaction temperature in the present invention 1 is too low, the reaction rate decreases, and if it is too high, the (meth) acryl group is polymerized.
• the reaction pressure is usually in the range of 0.01 to 0.1 MPa in absolute pressure. If it is this range, the apparatus of special withstand pressure
• the reaction time in the present invention 1 is usually 1 minute to 1 minute in the reaction of 1-adamantanecarboxylic acid ester with a metal organic compound and in the reaction of a reaction intermediate obtained by the above reaction with (meth) acrylic anhydride. It is in the range of 24 hours, preferably 10 minutes to 20 hours.
• the salt is removed by washing with water, followed by washing with a basic aqueous solution.
• a basic aqueous solution include aqueous solutions of inorganic basic compounds such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonia, and organic basic compounds such as ethylenediamine, aniline, triethylamine, and pyridine. An aqueous solution etc. are mentioned.
• 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. be able to. Of these, methanol is preferably used.
• GC gas chromatography
• LC liquid chromatography
• GC-MS gas chromatography mass spectrometry
• NMR nuclear magnetic resonance spectroscopy
• IR infrared spectroscopy It can be performed using a melting point measuring device or the like.
• R 4 , R 5 and X 2 are the same as described above.
• the metal alkoxide represented by the general formula (11) is a reaction intermediate produced by the reaction of 2-adamantanone and an organometallic compound.
• the 1-adamantyl alkyl alcohol represented by the general formula (12) is a byproduct (unreacted product) in the reaction between the reaction intermediate and (meth) acrylic anhydride.
• the adamantyl (meth) acrylate represented by the general formula (8) can also be produced by reacting (meth) acrylic anhydride with the 1-adamantyl alkyl alcohol represented by the general formula (12). .
• the 2-adamantanone represented by the general formula (5) is reacted with the metal organic compound represented by the general formula (6) or (7), and then the generated general formula It is carried out by reacting (meth) acrylic anhydride after adding the carboxylic acid ester compound to the reaction mixture containing the reaction intermediate represented by (11). These reactions are usually carried out in an organic solvent.
• the present invention 2 is characterized in that a (meth) acrylic anhydride is reacted after adding a carboxylic acid ester compound to a reaction mixture containing the reaction intermediate represented by the general formula (11).
• the 2-adamantanone used in the present invention 2 is represented by the following general formula (5).
• the 2-adamantanone represented by the general formula (5) can be obtained by oxidizing adamantane in sulfuric acid.
• the 2-adamantanone represented by the general formula (5) may contain impurities derived from equipment in the production process, production raw materials, and the like. Therefore, the metal component contained as an impurity can be removed by subjecting the 2-adamantanone to sublimation purification before being subjected to the reaction with the organometallic compound. As a result, the content of metal impurities in the obtained adamantyl (meth) acrylate can be reduced, and high-purity adamantyl (meth) acrylate can be obtained.
• sublimation purification is performed at normal pressure, a high temperature around 200 ° C.
• the temperature is usually 20 to 180 ° C, preferably 30 to 150 ° C.
• the pressure is preferably 0.1 to 100 mmHg (0.013 to 13.3 kPa), more preferably 5 to 50 mmHg (0.65 to 6.5 kPa). For example, if the pressure is reduced to 2.7 kPa, it can be performed at around 100 ° C.
• the organometallic compound used in the present invention 2 is represented by the following general formula (6) or (7).
• X 2 represents a halogen atom, and examples thereof include the same specific examples and preferred examples of X 1 described above.
• R 4 is the same as described above.
• Specific examples of the organometallic compounds represented by the general formulas (6) and (7) are the same as the organometallic compounds represented by the general formulas (2) and (3) described above. Of these, methyl magnesium chloride, ethyl magnesium chloride, isopropyl magnesium chloride, methyl lithium, ethyl lithium, and isopropyl lithium are preferable.
• the amount of the organometallic compound used is usually 1 to 3 mol, preferably 1 to 2 mol, more preferably 1 to 1.5 mol, per 1 mol of 2-adamantanone represented by the general formula (5). It is.
• the amount of the carboxylic acid ester compound used is from the number of moles of the organometallic compound represented by the general formula (6) or (7) from the viewpoint of suppressing the production of by-products and improving the selectivity of the target product.
• the range of 0.1 to 5.0 times mol is preferable with respect to the number of mols obtained by subtracting the number of mols of 2-adamantanone represented by the general formula (5), and 1.0 to 1.5 times mol. A range is more preferred.
• Specific examples and preferred examples of the organic solvent are the same as those described in the present invention 1.
• Specific examples of (meth) acrylic anhydride are the same as those described in the present invention 1.
• the amount of (meth) acrylic anhydride used is usually about 1 to 5 moles per mole of 2-adamantanone represented by the general formula (5).
• the reaction temperature in the present invention 2 can be appropriately selected depending on the kind of reaction components, but is preferably in the range of ⁇ 200 to 200 ° C. If the reaction temperature in the present invention 2 is too low, the reaction rate is lowered, and if it is too high, the (meth) acryl group is polymerized.
• the reaction pressure is usually in the range of 0.01 to 0.1 MPa in absolute pressure. If it is this range, the apparatus of special withstand pressure
• the reaction time in the present invention 2 is usually 1 minute to 24 hours in the reaction of 2-adamantanone with a metal organic compound and in the reaction of a reaction intermediate obtained by the above reaction with (meth) acrylic anhydride, respectively. Preferably, it is in the range of 10 minutes to 20 hours.
• the specific mode of the post-treatment after completion of the reaction in the present invention 2 is the same as that described in the present invention 1.
• Metal analysis was performed using an inductively coupled plasma mass spectrometer “ICP-MS 7500cs” (manufactured by Agilent).
• GC purity The purity of the product was measured by gas chromatography (GC).
• GC analysis was performed using an apparatus “GC-14A” manufactured by Shimadzu Corporation.
• Example 1 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 the temperature at 10 ° C. or lower, 247 g (494 mmol) of a 2M tetrahydrofuran (THF) solution of methylmagnesium chloride was added dropwise over 4.5 hours, and then allowed to react for 15 hours while naturally raising the temperature. Here, 9 g (102 mmol) of ethyl acetate was added and reacted at room temperature for 0.5 hour.
• THF tetrahydrofuran
• magnesium was decomposed with an aqueous hydrochloric acid solution, and the aqueous layer was separated. Subsequently, the mixture was washed with a 10% by mass aqueous sodium hydroxide solution and saturated brine, and then concentrated. The concentrate was crystallized from methanol to obtain 41 g of the desired 1- (1-adamantyl) -1-methylethyl methacrylate (isolation yield: 76%, GC purity: 99.7%). As a result of metal analysis of the obtained 1- (1-adamantyl) -1-methylethyl methacrylate, the detected amounts of Al, Ca, Fe, K, and Na were all 0.01 ppm or less.
• Example 4 The same procedure as in Example 1 was carried out except that 16 g of phenyl ethyl acetate was used instead of 9 g of ethyl acetate.
• Example 5 It implemented like Example 1 except having used 10 g of methyl methacrylate instead of 9 g of ethyl acetate.
• Example 1 was carried out in the same manner as Example 1 except that ethyl acetate was not added to obtain 1- (1-adamantyl) -1-methylethyl methacrylate.
• Comparative Example 4 In Comparative Example 2, it was carried out in the same manner as 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 GC peak of 1- (1-adamantyl) -1-methylethanol was observed, and the GC peak of the desired 1- (1-adamantyl) -1-methylethyl methacrylate was not observed, and the reaction did not proceed at all.
• Comparative Example 5 In Comparative Example 3, it was carried out in the same manner as Comparative Example 3 except that 0.12 mL (1.5 mmol) of pyridine was used instead of 0.21 mL (1.5 mmol) of triethylamine. Only the GC peak of 1- (1-adamantyl) -1-methylethanol was observed, and the GC peak of the desired 1- (1-adamantyl) -1-methylethyl methacrylate was not observed, and the reaction did not proceed at all.
• Example 6 150 g of THF was added to 4 g (600 mmol) of lithium and cooled to 5 ° C. or lower. A solution prepared by adding 30 g (200 mmol) of 2-adamantanone / 31 g (400 mmol) of isopropyl chloride / 300 g of THF was added dropwise over 1 hour, and the reaction was further continued for 1 hour while maintaining the temperature at 20 ° C. or lower. Here, 18 g (204 mmol) of ethyl acetate was added, and the reaction was further continued for 1 hour while maintaining the temperature at 20 ° C. or lower.
• the concentrate was crystallized from methanol to obtain 42 g of the desired 2-isopropyl-2-adamantyl methacrylate (isolation yield: 80%, GC purity: 99.8%).
• the detected amounts of Al, Ca, Fe, K, and Na were all 0.01 ppm or less.
• Example 7 The same procedure as in Example 6 was performed except that 20 g of methyl propionate was used instead of 18 g of ethyl acetate.
• Example 8 The same procedure as in Example 6 was performed except that 28 g of methyl benzoate was used instead of 18 g of ethyl acetate.
• Object 2-isopropyl-2-adamantyl methacrylate: 97.1%
• purification was conducted in the same manner as in Example 6 to obtain 42 g of the desired 2-isopropyl-2-adamantyl methacrylate (isolation yield: 80%, GC purity: 99.5%).
• the detected amounts of Al, Ca, Fe, K, and Na were all 0.01 ppm or less.
• Example 9 The same procedure as in Example 6 was performed except that 32 g of ethyl phenylacetate was used instead of 18 g of ethyl acetate.
• Example 10 The same procedure as in Example 6 was performed except that 20 g of methyl methacrylate was used instead of 18 g of ethyl acetate.
• Target product 2-isopropyl-2-adamantyl methacrylate: 97.5%
• purification was conducted in the same manner as in Example 6 to obtain 44 g of the desired 2-isopropyl-2-adamantyl methacrylate (isolation yield: 84%, GC purity: 99.5%).
• the detected amounts of Al, Ca, Fe, K, and Na were all 0.01 ppm or less.
• Example 7 Comparative Example 7 In Example 6, it carried out like Example 6 except not adding ethyl acetate.
• the crude reaction solution was purified in the same manner as in Example 6. The final product obtained was 29 g (isolation yield: 55%, GC purity: 99.0%).
• Comparative Example 8 In Comparative Example 7, the same procedure as in Comparative Example 7 was performed except that 31 g of methacrylic acid chloride was used instead of 46 g of methacrylic anhydride.

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