WO2013022015A1 - 含フッ素芳香族化合物およびその製造方法 - Google Patents
含フッ素芳香族化合物およびその製造方法 Download PDFInfo
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- WO2013022015A1 WO2013022015A1 PCT/JP2012/070153 JP2012070153W WO2013022015A1 WO 2013022015 A1 WO2013022015 A1 WO 2013022015A1 JP 2012070153 W JP2012070153 W JP 2012070153W WO 2013022015 A1 WO2013022015 A1 WO 2013022015A1
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- fluorine
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- 0 CCC(*)(C(C=C(*)C=C1)C=C1C(CC(C(F)(F)F)(C(F)(F)F)O)=CC(C(F)(F)F)(C(F)(F)F)O)C(C(F)(F)F)(C(F)(F)F)O Chemical compound CCC(*)(C(C=C(*)C=C1)C=C1C(CC(C(F)(F)F)(C(F)(F)F)O)=CC(C(F)(F)F)(C(F)(F)F)O)C(C(F)(F)F)(C(F)(F)F)O 0.000 description 14
- VKPSLEKTYOXJLJ-VMPITWQZSA-N OC(C/C(/c(cc1)ccc1O)=C\C(C(F)(F)F)(C(F)(F)F)O)(C(F)(F)F)C(F)(F)F Chemical compound OC(C/C(/c(cc1)ccc1O)=C\C(C(F)(F)F)(C(F)(F)F)O)(C(F)(F)F)C(F)(F)F VKPSLEKTYOXJLJ-VMPITWQZSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/373—Halogenated derivatives with all hydroxy groups on non-condensed rings and with unsaturation outside the aromatic rings
Definitions
- the present invention relates to a novel fluorine-containing aromatic compound and a method for producing the same.
- a novel fluorine-containing fragrance that provides excellent resist adhesion in lithography when it is converted into a polymerizable compound and then polymerized (polymerized) to form a resist material that is used with a photoacid generator or the like.
- the present invention relates to a group compound and a method for producing the same.
- Fluorine-containing compounds are used as functional materials taking advantage of characteristics such as water repellency, low water absorption, high heat resistance, corrosion resistance, transparency, low dielectric constant or low refractive index.
- a hexafluoroisopropanol group is known as a functional group that imparts moderate hydrophilicity in addition to low water absorption or transparency to polyolefins and condensed polymers.
- a hexafluoroisopropanol group that is, 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group: —C (CF 3 ) 2 OH (hereinafter sometimes referred to as HFIP group)
- HFIP group 2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl group: —C (CF 3 ) 2 OH
- Photolithography refers to exposing a substrate surface coated with a photoresist, which is a photosensitive substance, to a desired pattern.
- the photolithographic technique is a technique for forming a resist pattern on a substrate due to a difference in solubility between a exposed portion of a resist and an unexposed portion by a developer.
- phenols having an HFIP group are derivatized and synthesized into a polymerizable olefin monomer such as acrylate, methacrylate or vinyl ether by a selective nucleophilic substitution reaction at the phenol moiety.
- the polymerizable olefin monomer is useful as a resist composition.
- aniline containing an HFIP group can be derivatized and synthesized into acrylamide, methacrylamide, vinylamine or the like.
- Patent Document 1 discloses the following fluorine-containing polymerizable monomer containing an HFIP group.
- R 1 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
- N is 0 or 1
- m is an integer of 1 to (3 + n).
- R 2 and R 3 are And each independently represents a hydrogen atom or a protecting group.
- a polymer compound obtained by polymerizing these fluorine-containing polymerizable monomers and containing at least units composed of these fluorine-containing polymerizable monomers is useful as a resist composition.
- Patent Document 2 discloses a method in which compound B is nitrated, compound C is obtained, compound C is aminated, compound D is obtained, compound D is phenolized (hydroxy group added), and compound E is obtained. Has been.
- the compound E is polymerized with a fluorine-containing polymerizable monomer obtained by reacting with acrylic acid, methacrylic acid, or vinyl ether, and contains at least a site composed of these fluorine-containing polymerizable monomers.
- Molecular compounds are useful as resist compositions.
- Patent Document 1 The fluorine-containing polymerizable monomer described in Patent Document 1 in which the HFIP group is separated from the main chain of the polymer via a cyclohexane ring is easily produced.
- Patent Document 2 the compound described in Patent Document 2 is synthesized by a multistage reaction, and has a man-hour for production.
- Examples 3 to 6 of Patent Document 2 specifically describe synthesis examples of the following compounds (F) to (I) in which a double bond is introduced into the compound (E).
- Compounds (F) to (I) are polymerizable, and can be formed into resists by homopolymerization or copolymerization with other polymerizable compounds and then adding a photoacid generator or the like.
- Non-Patent Document 1 describes a reaction in which the isopropylidene bond (-C (CH 3 ) 2 -site) of bisphenol A is cleaved using sulfuric acid as an acid catalyst in the presence of sulfuric acid.
- a polymer resist in which the HFIP group is separated from the polymer main chain has excellent adhesion to the substrate and is soluble in an exposed or unexposed portion of the alkaline developer. The difference in insolubility is clear and gives a precise resist pattern.
- a polymer resist having a structure in which the HFIP group is located in the vicinity of the main chain of the polymer and the vicinity of the main chain is sterically crowded has a problem that the resist performance described above due to the inclusion of the HFIP group cannot be sufficiently exhibited.
- the present invention provides a fluorine-containing aromatic compound as a raw material for an HFIP group-containing polymer in which the HFIP group is located at a position away from the polymer main chain, which is produced by a simple method that solves the above-mentioned problems, and a method for producing the same. For the purpose.
- the present inventors have found that a novel fluorine-containing aromatic compound can be produced from bisphenol A and other aromatic compounds having an isopropylidene bond by a simple method, and have completed the present invention.
- the present invention includes the fluorine-containing aromatic compounds of Inventions 1 to 7 and the method for producing the fluorine-containing aromatic compounds of Inventions 8 to 14 for obtaining the fluorine-containing aromatic compounds of Inventions 1 to 7.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- a part or all of hydrogen atoms in the alkyl group may be substituted with fluorine atoms
- n is an integer of 0 to 2
- m and l are each independently 0 or 1
- R 2 is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a part or all of the hydrogen atoms in the alkyl group.
- the atom may be substituted with a fluorine atom, and m is 0 or 1.
- the fluorine-containing aromatic compound of the invention 1 or the invention 2 represented by these.
- a part or all of hydrogen atoms in the alkyl group may be substituted with a fluorine atom group, R 6 is a hydroxyl group or an amino group, and n is an integer of 0 to 2 .
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- n is an integer of 0 to 2
- m and l are each independently 0 or 1
- the fluorine-containing aromatic compound of the invention 1 represented by the general formula (1) is synthesized by the production method of the invention 8.
- the fluorine-containing aromatic compound of the invention 3 represented by the general formula (3) can be produced by the production method of the invention 10.
- the fluorine-containing aromatic compound of the invention 4 represented by the formula (4) can be produced by the production method of the invention 11.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- a part or all of hydrogen atoms in the alkyl group may be substituted with fluorine atoms, and R 6 is a hydroxyl group or an amino group.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- a part or all of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms, and m and l are each independently 0 or 1.
- the manufacturing method of the fluorine-containing aromatic compound of invention 8 represented by these.
- the fluorine-containing aromatic compound of the invention 6 represented by the general formula (6) can be produced by the method of the invention 13.
- the fluorine-containing aromatic compound of the invention 7 represented by the formula (7) can be produced by the production method of the invention 14.
- invention 15 The production method of inventions 8 to 14, wherein the acid catalyst is methanesulfonic acid.
- a novel fluorine-containing HFIP group-containing fluorine-containing aromatic process according to the present invention in which an isopropylidene bond of an aromatic compound containing bisphenol A and a derivative thereof is cleaved under acid catalyst and hexafluoroacetone is added. Aromatic compounds were easily obtained.
- the fluorine-containing reportable group compound is useful for resist applications.
- the fluorine-containing aromatic compound of the present invention contains an HFIP group in the structure.
- the present invention relates to a general formula (1):
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- a part or all of hydrogen atoms in the alkyl group may be substituted with fluorine atoms
- n is an integer of 0 to 2
- m and l are each independently 0 or It is a fluorine-containing aromatic compound represented by 1).
- R 1 is preferably a hydroxy group or an amino group.
- a functional group having a double bond at the site of the hydroxy group is obtained by the methods described in Patent Document 2 and Patent Document 3. It can introduce
- the polymerizable compound is reacted with acrylic acid, methacrylic acid or vinyl ether to form a fluorine-containing polymerizable monomer, polymerized with other functional monomers to form a polymer, and a photoacid generator is added to form a photoresist. be able to.
- the double bond on the HFIP group side has low reactivity, and the double bond of the functional group formed by substitution of the hydrogen atom of the hydroxy group is likely to undergo a polymerization reaction.
- fluorine-containing aromatic compound represented by the general formula (1) include the following compounds, but the present invention is not limited thereto.
- General formula (2) (In the formula (2), R 1 is a hydroxyl group or an amino group, and R 2 is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms. , A part or all of the hydrogen atoms may be substituted with fluorine atoms, and m is 0 or 1.)
- the fluorine-containing aromatic compound represented by the above is easy to synthesize and has one aromatic ring, When used as a raw material for a resist composition, the resulting resist is easily dissolved in an organic solvent, and handling in photolithography is good.
- R 1 is preferably an OH group, and a functional group having a double bond at the hydroxy group site is obtained by the methods described in Patent Document 2 and Patent Document 3. After being introduced to form a polymerizable compound, it can be reacted with acrylic acid or methacrylic acid.
- R 2 is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a part or all of the hydrogen atoms are fluorine atoms.
- the fluorine-containing aromatic compound represented by the formula (M) may be substituted, and m is 0 or 1.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms.
- a part or all of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms
- m and l are each independently 0 or 1. Since a fluorine aromatic compound is easy to synthesize and has two aromatic rings, the resulting resist is easily dissolved in an organic solvent when used as a raw material for a resist composition, and handling in photolithography is good.
- R 1 is preferably an OH group, and a functional group having a double bond at the hydroxy group site is obtained by the methods described in Patent Document 2 and Patent Document 3. After being introduced to form a polymerizable compound, it can be reacted with acrylic acid or methacrylic acid.
- R 2 to R 5 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 or 4 carbon atoms. Some or all of the hydrogen atoms may be substituted with fluorine atoms, and m and l are each independently 0 or 1.)
- the fluorine-containing aromatic compound represented by these is preferable.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms. A part of or all of the hydrogen atoms may be substituted with a fluorine atom group
- R 6 is a hydroxyl group or an amino group
- n is an integer of 0 to 2.
- Specific examples of the aromatic compound represented by formula (1) include the following compounds, but the present invention is not limited thereto.
- R 1 is a hydroxyl group or an amino group
- R 2 is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms
- R 6 is a hydroxyl group or an amino group.
- R 1 and R 6 are preferably OH groups, General formula (10):
- R 2 is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and a part or all of the hydrogen atoms in the alkyl group.
- the atom may be substituted with a fluorine atom.
- bisphenol A is a particularly preferable aromatic compound.
- R 1 is a hydroxyl group or an amino group
- R 2 to R 5 are each independently a hydrogen atom, a straight chain having 1 to 4 carbon atoms or a branched chain having 3 or 4 carbon atoms. And a part or all of the hydrogen atoms in the alkyl group may be substituted with a fluorine atom group, and R 6 is a hydroxyl group or an amino group.
- the fluorine-containing aromatic compound represented by the general formula (6) can be easily synthesized, and the fluorine-containing aromatic compound represented by the general formula (6) has two aromatic rings.
- the raw material is used, the resulting resist is easily dissolved in an organic solvent, and handling in photolithography is good.
- R 1 is preferably an OH group, and a functional group having a double bond at the hydroxy group site is obtained by the methods described in Patent Document 2 and Patent Document 3. After being introduced to form a polymerizable compound, it can be reacted with acrylic acid or methacrylic acid.
- R 1 is preferably an OH group
- R 2 to R 5 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, Some or all of the hydrogen atoms may be substituted with fluorine atom groups, and R 6 is preferably a hydroxyl group or an amino group.
- the method for producing a fluorine-containing aromatic compound of the present invention described in Inventions 8 to 14 is the same as the fluorine-containing aromatic compound represented by the above formula (4), that is, 1,1,1,7,7,7.
- the production method of hexafluoro-4- (4-hydroxyphenyl) -2,6-bis (trifluoromethyl) hept-3-yne-2,6-diol will be described in detail as an example.
- the method for producing a fluorine-containing aromatic compound of the present invention is not limited to the method for producing a fluorine-containing aromatic compound of Invention 11 for synthesizing the fluorine-containing aromatic compound represented by the formula (4).
- the fluorine-containing aromatic compound represented by the formula (4) is obtained by reacting bisphenol A with HFA or HFA trihydrate.
- HFA trihydrate bisphenol A and HFA trihydrate are mixed and reacted. Since the boiling point of HFA trihydrate is 105 ° C., it is easier to handle than HFA. At this time, a sealed vessel may be used as the reaction apparatus, but HFA trihydrate can be kept in the reaction system by water cooling using a reflux condenser.
- the amount of HFA or HFA trihydrate used when synthesizing the fluorinated aromatic compound of the present invention is preferably 2 molar equivalents or more and 5 molar equivalents or less, preferably 2 molar equivalents relative to bisphenol A. Above, it is below 3 molar equivalent. If the amount is less than 2 molar equivalents, the yield of the fluorine-containing aromatic compound represented by formula (4) is low, and the reaction proceeds even when used in excess of 5 molar equivalents, and the fluorine-containing aromatic compound represented by formula (4). Aromatic compounds are obtained but need not be used in excess of 5 molar equivalents.
- the reaction for synthesizing the fluorinated aromatic compound of the present invention can be carried out in a temperature range of 50 ° C. or more and 200 ° C. or less, but 60 ° C. or more and 130 ° C. or less is particularly preferable.
- the reaction is difficult to proceed at a temperature lower than 50 ° C., and at a temperature higher than 200 ° C., particularly 250 ° C. or higher, the yield of the fluorine-containing aromatic compound represented by the formula (4) decreases.
- acid catalysts used include Lewis acid such as aluminum chloride, iron (III) chloride or boron fluoride, organic sulfonic acid such as benzenesulfonic acid, camphorsulfonic acid (CSA), methanesulfonic acid, and p-toluenesulfonic acid.
- Lewis acid such as aluminum chloride, iron (III) chloride or boron fluoride
- organic sulfonic acid such as benzenesulfonic acid, camphorsulfonic acid (CSA), methanesulfonic acid, and p-toluenesulfonic acid.
- PTsOH p-toluenesulfonic acid
- pTsOH p-toluenesulfonic acid
- PPTS pyridinium p-toluenesulfonic acid
- aluminum chloride, iron (III) chloride, methanesulfonic acid, p-toluenesulfone Acid (pTsOH) monohydrate is preferable, and methanesulfonic acid is particularly preferable.
- the amount of the acid catalyst used is 1 mol% or more and 50 mol% or less, preferably 3 mol% or more and 40 mol% or less, relative to 100 mol% of bisphenol A. If it is less than 1 mol%, the yield of the fluorine-containing aromatic compound represented by formula (4) is low, and the reaction proceeds even if it is used in an amount of more than 50 mol%, but it is not necessary to add much.
- the reaction may be solvent-free, but it is preferable to use a solvent because of good handling.
- the solvent used is not particularly limited as long as it does not participate in the reaction, but aromatic hydrocarbons such as xylene, toluene, benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, chlorinated solvents such as chloroform and methylene chloride. Dichloroethane, dichlorobenzene, water or hexafluoroisopropanol ((CF 3 ) 2 HC—OH) is preferred.
- the amount of the solvent to be used is not particularly limited, but the use of a large amount is not preferable because the yield of the fluorinated aromatic compound represented by the general formula (4) per unit volume of the reactor is reduced.
- the mode differs depending on either HFA or HFA trihydrate.
- HFA HFA trihydrate
- HFA trihydrate bisphenol A and HFA trihydrate are first put in a reactor, and a reaction can be carried out by adding a catalyst or a solvent.
- reaction time of the reaction is not particularly limited, but it is appropriately selected depending on the temperature or the amount of catalyst used. Therefore, it is preferable to terminate the reaction after confirming that the raw material has been sufficiently consumed by general-purpose analysis means such as gas chromatography.
- general-purpose analysis means such as gas chromatography.
- the fluorine-containing aromatic compound represented by the formula (4) can be obtained by means such as extraction, distillation, crystallization and the like. If necessary, the fluorine-containing aromatic compound represented by the formula (4) can be purified by column chromatography or recrystallization.
- the fluorine-containing aromatic compound having an HFIP group of the present invention obtained by the method for producing a fluorine-containing aromatic compound of the present invention is an aromatic compound having an isopropylidene bond containing bisphenol A or a derivative thereof.
- the fluorinated aromatic compound of the present invention derived from inexpensive bisphenol A is useful because it is easier to produce than the conventional fluorinated compounds used in photoresists.
- a functional group having a double bond is introduced into the fluorine-containing aromatic compound containing an HFIP group of the present invention by the method described in Patent Document 2 and Patent Document 3 to obtain a fluorine-containing polymerizable monomer, and then polymerized.
- a high molecular compound can be obtained. If this is used as a resist composition, the HFIP group is at a position away from the polymer main chain, and an excellent resist may be obtained.
- the identification method of the synthesized fluorine-containing aromatic compound is shown in the following (1) and (2).
- NMR Nuclear Magnetic Resonance
- Example 2 Synthesis of Fluorinated Aromatic Compound Represented by Structural Formula (7)
- room temperature 20 ° C.
- 15 g (0.04 mol) of the compound (13), 200 g of hexafluoroisopropanol, and 0.3 g of methanesulfonic acid as an acidic catalyst (2 to the compound (13)) Mass%) and 28.7 g (0.17 mol) of HFA were added, and then the temperature was gradually raised and stirred at 55 ° C. for 8 hours to proceed the following reaction.
- the solvent hexafluoroisopropanol was distilled off to obtain a solid, and NMR and mass spectrometry were performed.
- the fluorine-containing aromatic compound represented by the formula (7) was 80% by mass relative to the theoretical yield. It was confirmed that it was obtained in high yield. That is, the fluorine-containing aromatic compound represented by the formula (7) was obtained with high purity.
Abstract
Description
一般式(1):
で表される、含フッ素芳香族化合物。
一般式(2):
で表される、発明1に記載の含フッ素芳香族化合物。
一般式(3):
で表される、発明1または発明2の含フッ素芳香族化合物。
一般式(5):
で表される、発明1の含フッ素芳香族化合物。
一般式(6):
で表される、発明1または発明5の含フッ素芳香族化合物。
一般式(8):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させることを特徴とする、
一般式(1):
で表される、含フッ素芳香族化合物の製造方法。
一般式(9):
で表される芳香族化合物とへキサフルオロアセトンを、酸触媒下で反応させて、
一般式(2):
で表される、発明8の含フッ素芳香族化合物の製造方法。
一般式(10):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させて、
一般式(3):
で表される、発明8または発明9の含フッ素芳香族化合物の製造方法。
一般式(11):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させて、
一般式(5):
で表される、発明8に記載の含フッ素芳香族化合物の製造方法。
一般式(12):
一般式(6):
で表される、発明8または発明12の含フッ素芳香族化合物の製造方法。
酸触媒がメタンスルホン酸であることを特徴とする発明8~14の製造方法。
本発明の含フッ素芳香族化合物は、構造中に、HFIP基を含む。
一般式(2):
で表される含フッ素芳香族化合物が好ましい。
一般式(1)~(3)、式(4)、一般式(5)もしくは(6)、または式(7)で表される含フッ素芳香族化合物は、夫々に一般式(8)~(10)で表される化合物、ビスフェノールA、一般式(11)もしくは(12)または式(13)で表される芳香族化合物を原料(反応物)として、ヘキサフルオロアセトンと酸触媒下で反応させることで合成される。
で表される芳香族化合物を具体的に例示するならば、下記化合物が挙げられるが、本発明はこれらに限定されるものではない。
一般式(9):
一般式(10):
で表される芳香族化合物を用いることが好ましい。
一般式(11):
一般式(12):
本発明のHFIP基を有する新規な含フッ素芳香族化合物を得る製造方法は、酸触媒存在下で、芳香族化合物中のイソプロピリデン結合を酸触媒により切断し、さらにHFAを付加させ、HFIP基を得るものである。
式(4)で表される含フッ素芳香族化合物は、ビスフェノールAと、HFAもしくはHFA三水和物を反応させることによって得られる。
合成した含フッ素芳香族化合物の同定手法を以下の(1)、(2)に示す。
共鳴周波数400MHzの核磁気共鳴装置(日本電子株式会社製)を使用し、1H-NMR、19F-NMRの測定を行った。
質量分析計(日本電子株式会社製、品番、JMS-T100GC)を使用し、質量分析スペクトルを測定した。
[構造式(4)で表される含フッ素芳香族化合物(1,1,1,7,7,7-ヘキサフルオロ-4-(4-ヒドロキシフェニル)-2,6-ビス(トリフルオロメチル)ヘプト-3-イン-2,6-ジオール)の合成]
1H-NMR(溶媒d-DMSO,TMS):δ3.63(2H,s),5.49 (1H,s),6.71(2H,d,J=85Hz),7.16(2H,d,J=8.5Hz),9.58(1H,s)
19F-NMR(溶媒、d-DMSO、CCl3F):δ-74.8(6F,s),-73.4(6F,s)
Mass: (m/z) 466.04(M+)
[構造式(7)で表される含フッ素芳香族化合物の合成]
ステンレス鋼製のオートクレーブに、室温(20℃)で、化合物(13)15g(0.04mol)、ヘキサフルオロイソプロパノール200g、および酸性触媒として、メタンスルホン酸0.3g、(化合物(13)に対し2質量%)を入れ、HFA28.7g(0.17mol)を加えた後、徐々に昇温させ55℃で8時間攪拌し以下の反応を進行させた。反応終了後、溶媒であるヘキサフルオロイソプロパノールを留去し、固形物を得、NMR、質量分析を行い、式(7)で表される含フッ素芳香族化合物が理論収量に対し、80質量%の高い収率で得られたことを確認した。即ち、式(7)で表される含フッ素芳香族化合物が高い純度で得られた。
1H-NMR(溶媒、重アセトン、TMS)2.03(6H,s),7.01(4H,m),7.40(4H,m),8.31(1H,s),10.36(1H,s)19F-NMR(溶媒、重アセトン、CCl3F)-74.8(6F,s),-74.9(12F,s)
Mass : (m/z)750.14(M+)
Claims (15)
- 一般式(8):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させる、
一般式(1):
で表される、含フッ素芳香族化合物の製造方法。 - 一般式(9):
で表される芳香族化合物とへキサフルオロアセトンを、酸触媒下で反応させて、
一般式(2):
で表される、請求項8に記載の含フッ素芳香族化合物の製造方法。 - 一般式(11):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させて、
一般式(5):
で表される、請求項8に記載の含フッ素芳香族化合物の製造方法。 - 一般式(12):
で表される芳香族化合物とヘキサフルオロアセトンを、酸触媒下で反応させて、
一般式(6):
で表される、請求項8または請求項12に記載の含フッ素芳香族化合物の製造方法。 - 酸触媒がメタンスルホン酸であることを特徴とする請求項8乃至請求項14のいずれか1項に記載の製造方法。
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CN201280037594.2A CN103717561B (zh) | 2011-08-09 | 2012-08-08 | 含氟芳香族化合物及其制造方法 |
US14/237,651 US8981163B2 (en) | 2011-08-09 | 2012-08-08 | Fluorine-containing aromatic compound and method for producing same |
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JP4052807B2 (ja) * | 2001-03-02 | 2008-02-27 | セントラル硝子株式会社 | 含フッ素環状化合物 |
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KR100562442B1 (ko) * | 2002-08-07 | 2006-03-17 | 샌트랄 글래스 컴퍼니 리미티드 | 항반사광 필름재료 및 레지스트 조성물용 플로린 함유 화합물 및 그의 폴리머 |
JP2004099689A (ja) * | 2002-09-06 | 2004-04-02 | Central Glass Co Ltd | 含フッ素多環式化合物、それを原料とした高分子化合物、及びそれを用いたフォトレジスト材料 |
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CN103717561A (zh) | 2014-04-09 |
KR101559855B1 (ko) | 2015-10-13 |
JP2013053139A (ja) | 2013-03-21 |
US20140194655A1 (en) | 2014-07-10 |
JP5971016B2 (ja) | 2016-08-17 |
US8981163B2 (en) | 2015-03-17 |
KR20140048291A (ko) | 2014-04-23 |
CN103717561B (zh) | 2015-08-26 |
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