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WO2013018302A1 - Procédé pour produire de l'éther vinylique aromatique - Google Patents

Procédé pour produire de l'éther vinylique aromatique Download PDF

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Publication number
WO2013018302A1
WO2013018302A1 PCT/JP2012/004601 JP2012004601W WO2013018302A1 WO 2013018302 A1 WO2013018302 A1 WO 2013018302A1 JP 2012004601 W JP2012004601 W JP 2012004601W WO 2013018302 A1 WO2013018302 A1 WO 2013018302A1
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vinyl ether
bis
aromatic vinyl
hydroxyphenyl
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Japanese (ja)
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隆一 天神林
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Maruzen Petrochemical Co Ltd
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Maruzen Petrochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • the present invention relates to a method for producing an aromatic vinyl ether, and particularly relates to a method for producing an aromatic vinyl ether having a structure in which a hydrogen atom of a phenolic hydroxyl group in an aromatic group is substituted with a vinyl group.
  • Vinyl ethers are useful compounds that are used as monomers for cationic polymerization and as intermediates for medical and agrochemical products.
  • the vinyl ethers are industrially produced by a reaction (Leppe reaction) of acetylene and alcohols using an alkali metal hydroxide or an alkali metal alcoholate as a catalyst.
  • Vinylation of the phenolic hydroxyl group can be performed by performing the reaction at a high acetylene pressure (20 to 50 atm) (for example, see Non-Patent Document 1).
  • acetylene has decomposition and explosive properties, and the higher the pressure, the greater the danger. Therefore, the reaction at high pressure is difficult to implement industrially.
  • Non-patent Document 2 a vinyl exchange reaction between an aryl alcohol and a vinyl acetate using a transition metal catalyst
  • HBr from ⁇ -bromoether a vinyl exchange reaction between an aryl alcohol and a vinyl acetate using a transition metal catalyst
  • a desorption reaction Non-patent Document 3
  • a dehydration reaction from ethylene glycol monoether using a solid catalyst Patent Document 2
  • the present invention relates to a method for producing an aromatic vinyl ether having a structure in which a hydrogen atom of a phenolic hydroxyl group in an aromatic group is substituted with a vinyl group, and various methods can be performed safely with a simple apparatus without using an expensive catalyst.
  • An object of the present invention is to provide a method for producing an aromatic vinyl ether capable of producing various kinds of the aromatic vinyl ether.
  • R and n have the same meanings as those in formula (1) ⁇ , which is converted into an aromatic vinyl ether (2) having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a vinyl group.
  • various aromatic vinyl ethers having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a vinyl group which is difficult to produce by a conventional method, can be easily prepared without using an expensive catalyst. Safe to manufacture with equipment.
  • FIG. 2 is a 1 H-NMR chart of 9,9-bis- (4-vinyloxyphenyl) fluorene obtained in Example 4.
  • FIG. 3 is a 13 C-NMR chart of 9,9-bis- (4-vinyloxyphenyl) fluorene obtained in Example 4.
  • FIG. 4 is an IR chart of 9,9-bis- (4-vinyloxyphenyl) fluorene obtained in Example 4.
  • the aromatic vinyl ether (1) which is a raw material and has a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a vinyloxyethyl group, is represented by the above formula (1).
  • the residue of phenol having a phenolic hydroxyl group means “a structure obtained by removing hydrogen from the phenolic hydroxyl group of phenol”, and n is an integer of 1 to 3.
  • the residues of phenols having n phenolic hydroxyl groups represented by R include, for example, monovalent phenol residues represented by the following formula (I) or formula (II), the following formulas (III), ( IV) or a residue of a divalent phenol represented by (V), or a residue of a trivalent phenol represented by the following formula (VI), (VII), (VIII) or (IX).
  • the phenolic hydroxyl group may be bonded to the same aromatic ring or different aromatic rings.
  • X represents a single bond, —O—, —CR 5 R 6 —, —O—CR 7 R 8 —, —CR 9 R 10 —.
  • O— wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms
  • 24 is an aryl group
  • —O—R 11 —O— wherein R 11 is methylene or an alkylene group having 2 to 6 carbon atoms), an ⁇ , ⁇ -alkylene group having 2 to 12 carbon atoms, carbon A cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, or a 9,9-fluorenylidene group, wherein R 1
  • R 3 is a naphthylene group substituent, which is a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a carbon An aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and c is an integer of 0 to 6.
  • Y represents a trivalent alkyl group having 1 to 6 carbon atoms, a trivalent alicyclic hydrocarbon group having 5 to 15 carbon atoms, or a trivalent aromatic carbon group having 6 to 20 carbon atoms.
  • R 4 is a substituent of a phenylene group, and is a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • Group, an aryloxy group having 6 to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, d is an integer of 0 to 4, and a plurality of R 4 and d may be the same or different.
  • alkyl group having 1 to 12 carbon atoms in R 5 , R 6 , R 7 , R 8 , R 9 and R 10 for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group, n-octyl group Group, n-decyl group, n-dodecyl group and the like.
  • Examples of the aryl group having 6 to 24 carbon atoms in R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a phenyl group, a 2-tolyl group, a 3-tolyl group, and a 4-tolyl group.
  • alkylene group having 2 to 6 carbon atoms in R 11 for example, ethylene, ethane-1,1-diyl, propylene, Propane-2,2-diyl, 1-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, butylene, 1-methylbutylene, 2-methylbutylene , 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene and the like.
  • examples of the ⁇ , ⁇ -alkylene group having 2 to 12 carbon atoms in X include ethylene, propylene, 1-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 2,2-dimethylpropylene, , 3-dimethylpropylene, butylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene Etc.
  • Examples of the cycloalkylene group having 5 to 12 carbon atoms in X include a monocycloalkylene group such as a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group, and an alkyl-substituted product thereof; Examples include polycycloalkylene groups such as bicyclopentylene group, bicyclohexylene group, bicycloheptylene group, bicyclooctylene group, bicyclononylene group, bicyclodecylene group, tricyclodecylene group, and alkyl-substituted products thereof.
  • alkyl group to be added to the cycloalkylene group examples include an alkyl group having 1 to 6 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group and the like.
  • the number of substituents is not limited to 1, and when they have a plurality of substituents, they may be the same or different.
  • Examples of the cycloalkylidene group having 5 to 12 carbon atoms in X include, for example, a monocycloalkylidene group derived from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane and the like; Examples thereof include polycycloalkylidene groups derived from cyclodecane, dicyclopentadiene, norbornene, and alkyl-substituted products thereof.
  • Examples of the alkyl group to be added to the cycloalkylidene group include an alkyl group having 1 to 6 carbon atoms.
  • the number of substituents is not limited to 1, and when they have a plurality of substituents, they may be the same or different.
  • Examples of the trivalent alkyl group having 1 to 6 carbon atoms for Y in the formula (IX) include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane and the like. And a group obtained by removing three hydrogen atoms from a straight-chain or branched alkane having 1 to 6 carbon atoms.
  • Examples of the trivalent alicyclic hydrocarbon group having 5 to 15 carbon atoms in Y include a group in which 3 hydrogen atoms are removed from a monocyclic or polycyclic cycloalkane having 5 to 15 carbon atoms or an alkyl substituent thereof. Can be mentioned.
  • the hydrogen atom to be removed may be a cycloalkane or an added alkyl group.
  • a monocycloalkane such as cyclopentane or cyclohexane or an alkyl substituent thereof
  • a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like
  • the alkyl group to be added to the cycloalkane include an alkyl group having 1 to 6 carbon atoms.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec- Examples include a butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isoamyl group, and an n-hexyl group.
  • the number of substituents is not limited to 1, and when having a plurality of substituents, they may be the same or different.
  • Examples of the trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms in Y include, for example, an aromatic compound such as benzene, naphthalene, anthracene, phenanthrene, and pyrene, or a group obtained by removing three hydrogen atoms from an alkyl substituent thereof. Etc.
  • the hydrogen atom to be removed may be an aromatic compound or an added alkyl group.
  • alkyl group added to the aromatic compound examples include an alkyl group having 1 to 6 carbon atoms, and specifically include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group and the like.
  • the number of substituents is not limited to 1, and when having a plurality of substituents, they may be the same or different.
  • examples of the alkyl group having 1 to 12 carbon atoms in R 1 , R 2 , R 3 and R 4 include, for example, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, etc. .
  • Examples of the aryl group having 6 to 12 carbon atoms in R 1 , R 2 , R 3 and R 4 include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, and 2,3-xylyl.
  • Examples of the alkoxy group having 1 to 12 carbon atoms in R 1 , R 2 , R 3 and R 4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, Examples thereof include t-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group and the like.
  • Examples of the aryloxy group having 6 to 12 carbon atoms in R 1 , R 2 , R 3 and R 4 include a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2, 3 -Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5 -Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6 Tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butyl
  • Examples of the aralkyl group having 7 to 20 carbon atoms in R 1 , R 2 , R 3 and R 4 include a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methyl Phenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, ( 3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2, 3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethyl) Phenyl)
  • phenol residues represented by the above formulas (I) to (IX) preferred phenol residues are monophenol residues represented by formula (I) or formula (II), and m is 1 in formula (III). And a trisphenol residue represented by formula (VIII) or formula (IX).
  • the aromatic vinyl ether (1) containing a phenol residue represented by these formulas has only one reaction site (vinyloxyethoxy group) in one aromatic ring derived from the phenol structure, and one aromatic The reaction can be performed more stably than a compound having two or more reactive sites in the ring.
  • preferred residues include a monophenol residue represented by the formula (I) and a bisphenol residue represented by m in the formula (III) of 1 to 3.
  • the aromatic vinyl ether (1) containing these phenol residues has 1 to 2 vinyloxyethoxyphenyl groups in the molecule, and is more preferable in terms of reactivity.
  • Suitable monophenol residues represented by the formula (I) include phenol residues (phenoxy group); o-cresol, m-cresol, p-cresol, 3,5-xylenol, o- Ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-butylphenol, m-butylphenol, p-butylphenol, thymol (5-methyl-2-isopropylphenol) ), Residues of alkylphenols such as carvacrol (2-methyl-5-isopropylphenol), 2,6-diisopropylphenol, 3,5-diisopropylphenol; o-phenylphenol, m-phenylphenol, p-phenylphenol Such as phenyl Etc. residues of phenol compounds and the like.
  • suitable monophenol residues represented by the formula (II) include naphthol residues such as 1-naphthol and 2-naphthol; 2-methyl-1-naphthol, 3-methyl-1-naphthol 4-methyl-1-naphthol, 5-methyl-1-naphthol, 6-methyl-1-naphthol, 7-1-naphthol, 8-methyl-1-naphthol, 2,3-dimethyl-1-naphthol, 2 , 4-dimethyl-1-naphthol, 2,5-dimethyl-1-naphthol, 2,6-dimethyl-1-naphthol, 5,7-dimethyl-1-naphthol, 6,7-dimethyl-1-naphthol, , 5,8-trimethyl-1-naphthol, 1-methyl-2-naphthol, 6-methyl-2-naphthol, 7-methyl-2-naphthol
  • suitable bisphenol residues in which m is 1 to 3 include those in the formula (III) where X is a single bond, —O—, —CR 5 R 6 —, —O—R 11 And —O—, an ⁇ , ⁇ -alkylene group having 2 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, or a 9,9-fluorenylidene group.
  • bisphenol residue in which X is a single bond examples include 4,4′-biphenol, 3,3′-dimethyl-4,4′-biphenol, and 3,3 ′, 5,5′-tetramethyl.
  • Examples include residues of biphenols such as 5,5′-tetra-tert-butyl-2,2′-biphenol and derivatives thereof.
  • the derivative said here means what substituted the alkyl group, the halogen atom, etc. in the aromatic ring (Hereafter, it is the same in this
  • bisphenol residue in which X is —O— examples include 4,4′-dihydroxydiphenyl ether (4,4′-oxydiphenol), bis (3-methyl-4-hydroxyphenyl) ether, bis Examples include residues of oxydiphenols such as (3,5-dimethyl-4-hydroxyphenyl) ether and derivatives thereof.
  • X is —CR 5 R 6 — (wherein R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms)
  • residues of bisphenols represented by 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, , 1-bis (3,5-ditert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disecbutyl-4-hydroxyphenyl) methane, 1,1-bis (3- Nonyl-4-hydroxyphenyl) methane, 1,1-bis (3-fluoro-4-hydroxyphenyl) methane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) methane,
  • Examples of bisphenols in which X is an ⁇ , ⁇ -alkylene group having 2 to 12 carbon atoms include 1,2-bis (4-hydroxyphenyl) ethane, 1,2-bis (2-hydroxyphenyl) ethane, 1,2 And ethylene bisphenols such as bis (3,5-ditert-butyl-4-hydroxyphenyl) ethane and derivatives thereof.
  • bisphenols wherein X is —O—R 11 —O— include 3,3′-ethylenedioxy Diphenol, 2,2'-ethylenedioxydiphenol, ethylene glycol bis (3-hydroxy-5-methylphenyl) ether, ethylene glycol bis (2-hydroxy-5-methylphenyl) ether, ethylene glycol bis (2- Examples include residues of oxyalkylene bisphenols such as hydroxy-3,5-dimethylphenyl) ether and derivatives thereof.
  • bisphenol residue in which X is a cycloalkylidene group having 5 to 12 carbon atoms include 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • bisphenol residue in which X is a 9,9-fluorenylidene group include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene.
  • residues of fluorene bisphenols such as 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis (2-phenyl-4-hydroxyphenyl) fluorene, and derivatives thereof.
  • Suitable trisphenol residues represented by the formula (VIII) include ⁇ , ⁇ -bis (4-hydroxyphenyl) -2,6-diisopropylphenol, ⁇ , ⁇ -bis (4-hydroxy). And residues of ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylphenols such as phenyl) -3,4-diisopropylphenol and ⁇ , ⁇ -bis (4-hydroxyphenyl) -3,5-diisopropylphenol. .
  • trisphenol residue represented by the formula (IX) specifically, 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (4-hydroxyphenyl) propane, 1,1,1 Residues of tris (hydroxyphenyl) alkanes such as tris (2-hydroxyphenyl) methane, 1,1,1-tris (2-hydroxyphenyl) ethane, 2,2 ′, 4 ′′ -methylidynetrisphenol ; Residues of tris (hydroxyphenyl) cycloalkanes such as 4,4 ′, 4 ′′-(adamantane-1,3,5-triyl) trisphenol; 3,3 ′, 3 ′′-[(benzene-1,3,5-triyl) trismethylene] trisphenol, 3,3 ′, 3 ′′-[(2,4,6-trimethylbenzene-1,3 , 5-triyl)
  • phenol residues phenol residues, alkylphenol residues, phenylphenol residues, biphenols and derivatives thereof, bis (hydroxyphenyl) alkanes and derivatives thereof, bis ( Residues of hydroxyphenyl) phenylalkanes and derivatives thereof, residues of cycloalkylidene bisphenols and derivatives thereof, and residues of fluorene bisphenols and derivatives thereof are preferred, phenol residues, residues of alkylphenols, bis ( Residues of hydroxyphenyl) alkanes and derivatives thereof, and residues of fluorene bisphenols and derivatives thereof are more preferred.
  • raw material aromatic vinyl ether (1) represented by the above formula (1) include compounds represented by the following formulas (1-1) to (1-28).
  • the aromatic vinyl ether (2) having a structure in which the hydrogen atom of the obtained phenolic hydroxyl group is substituted with a vinyl group is vinyloxy. It has the same structure as the aromatic vinyl ether (1) except that the ethoxy group is converted to a vinyloxy group, and is represented by the above formula (2).
  • Specific examples of the aromatic vinyl ether (2) include compounds represented by the following formulas (2-1) to (2-28).
  • aromatic vinyl ether (1) as a raw material, a commercially available product may be used, or it may be produced by a known method.
  • Known methods include addition reaction of the corresponding aromatic alcohol and acetylene, vinyl exchange reaction of aryl alcohol and vinyl acetate, elimination reaction of HBr from ⁇ -bromoether, etc.
  • the reaction of acetylene and aromatic alcohol is more preferable in terms of the properties and the ability to synthesize various vinyl ethers.
  • R and n have the same meanings as those in the formula (1) ⁇ , using an alkali metal hydroxide or an alkali metal alcoholate as a catalyst under a low acetylene pressure (usually 0.3 MPa)
  • the following reaction method is preferred. According to this method, it is possible to use the obtained aromatic vinyl ether as the raw material aromatic vinyl ether (1) of the present invention without isolating it, and from the aromatic alcohol (3) to the raw material aromatic vinyl ether ( The reaction for obtaining 1) and the reaction of the present invention for obtaining the desired aromatic vinyl ether (2) from the starting aromatic vinyl ether (1) can be carried out in the same pot.
  • the alkali metal compound (alkali catalyst) used as a catalyst is alkali metal hydroxide such as potassium hydroxide or sodium hydroxide.
  • alkali metal alcoholates such as sodium ethylate, sodium methylate, tert-butoxy sodium, and tert-butoxy potassium.
  • potassium hydroxide and potassium alcoholate are preferable in terms of reactivity, and potassium hydroxide and tert-butoxy potassium are particularly preferable.
  • the amount of the alkali catalyst used is usually in the range of 0.2 to 2 mole times, preferably 0.5 to 1 mole times the amount of the aromatic vinyl ether (1) as the raw material.
  • the reaction temperature varies depending on the type of aromatic vinyl ether (1) as a raw material and the contact time with the catalyst, but is usually in the range of 50 to 200 ° C, preferably in the range of 80 to 150 ° C.
  • the reaction time is usually about 2 to 24 hours, preferably about 5 to 12 hours.
  • the reaction can be carried out without solvent or in the presence of a solvent.
  • the solvent is preferably an aprotic polar solvent that is miscible with the aromatic vinyl ether as a raw material and dissolves the alkali catalyst.
  • amide solvents such as dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; sulfur-containing compound solvents such as sulfolane and dimethyl sulfoxide; diethylene glycol Glycol dialkyl ethers such as dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether are used.
  • dimethyl sulfoxide N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethylene glycol dimethyl ether and the like are preferable from the viewpoint of reaction rate.
  • These solvents may be used alone or in combination of two or more.
  • reaction product obtained by the above method is separated by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination means combining these. Can be purified.
  • Example 1 Production of phenyl vinyl ether ⁇ 1> 1. (Production of 2-phenoxyethyl vinyl ether) 2-Phenoxyethyl vinyl ether as a raw material was synthesized by the following reaction.
  • Example 2 Production of phenyl vinyl ether ⁇ 2> 1.
  • 2-phenoxyethyl vinyl ether In a 1 L SUS pressure vessel equipped with a stirrer, pressure gauge, gas introduction line, gas purge line, and sampling line, 2-phenoxyethanol 100.0 g (0.72 mol), dimethyl sulfoxide 400.0 g (5.11 mol), Potassium hydroxide (8.8 g, 0.14 mol) was added, and the system was replaced with nitrogen gas while stirring at a rotational speed of 600 rpm. Subsequently, after the temperature of the reaction solution was set to 100 ° C., the inside of the system was replaced with acetylene gas, and the reaction was performed at 100 ° C.
  • Example 3 Production of phenyl vinyl ether ⁇ 3> 1.
  • 2-phenoxyethyl vinyl ether In a pressure vessel made of SUS with an internal volume of 1 L equipped with a stirrer, pressure gauge, gas introduction line, gas purge line, and sampling line, 100.0 g (0.72 mol) of 2-phenoxyethanol, 1,3-dimethyl-2-imidazolidinone 400.0 g (3.50 mol) and potassium hydroxide 8.8 g (0.14 mol) were added, and the system was replaced with nitrogen gas while stirring at a rotation speed of 600 rpm. Thereafter, the reaction solution temperature was raised to 120 ° C. and held for 1 hour.
  • a vacuum pump was connected to the gas purge line via a cooler, and the dehydration reaction was performed by gradually reducing the pressure from normal pressure to 2.5 kPa, thereby preparing an alcoholate catalyst.
  • the inside of the system was replaced with acetylene gas, and the reaction was carried out at 120 ° C. for 3.5 hours while continuously supplying acetylene at a pressure of 0.04 MPa.
  • the conversion rate of the raw material was 100%
  • the yield of 2-phenoxyethyl vinyl ether was 79.9%
  • the yield of phenyl vinyl ether was 8.1%.
  • Example 4 Production of phenyl vinyl ether ⁇ 4> 1.
  • 2-phenoxyethyl vinyl ether In a 1 L SUS pressure vessel equipped with a stirrer, pressure gauge, gas introduction line, gas purge line and sampling line, 50.0 g (0.36 mol) of 2-phenoxyethanol, 450.0 g of 1-methyl-2-pyrrolidone ( 4.54 mol) and 8.1 g (0.07 mol) of tert-butoxypotassium were added, and the system was replaced with nitrogen gas while stirring at a rotational speed of 600 rpm. Thereafter, the temperature of the reaction solution was set to 100 ° C., the inside of the system was replaced with acetylene gas, and the reaction was performed at 100 ° C.
  • Comparative Example 1 Production of phenyl vinyl ether 50.0 g (0.53 mol) of phenol and 450.7 g of dimethyl sulfoxide in a 1 L SUS pressure-resistant vessel equipped with a stirrer, pressure gauge, gas introduction line, gas purge line and sampling line (5.76 mol) and 6.0 g (0.11 mol) of potassium hydroxide were added, and the system was replaced with nitrogen gas while stirring at a rotational speed of 600 rpm. Subsequently, after the temperature of the reaction solution was set to 140 ° C., the inside of the system was replaced with acetylene gas, and maintained at 140 ° C. for 10 hours while maintaining the pressure at 0.04 MPa. The reaction solution was analyzed by gas chromatography, and it was confirmed that the raw materials were not reduced at all.
  • phenolic hydroxyl group of phenol is difficult to vinylate with acetylene, and phenyl vinyl ether cannot be obtained using phenol as a raw material.
  • phenyl vinyl ether can be obtained by vinylating 2-phenoxyethanol using acetylene and further converting the vinyloxyethoxy group into a vinyloxy group by the method of the present invention.
  • Example 5 Production of 9,9-bis- (4-vinyloxyphenyl) fluorene 9,9 in a 1 L SUS pressure-resistant vessel equipped with a stirrer, pressure gauge, gas introduction line, gas purge line and sampling line Add 100.1 g (0.23 mol) of bis- (4- (2-hydroxyethoxy) phenyl) fluorene, 400.9 g (5.13 mol) of dimethyl sulfoxide, 2.7 g (0.05 mol) of potassium hydroxide, and rotate. The system was replaced with nitrogen gas while stirring at several 600 rpm.
  • reaction solution temperature was 100 ° C. for 3 hours, and 10.5 g (0.19 mol) of potassium hydroxide was added and heated for 10 hours. Furthermore, 13.2 g (0.24 mol) of potassium hydroxide was added, and the reaction solution internal temperature was set to 120 ° C. and heated for 7 hours.
  • the reaction solution was placed in a 1 L separatory funnel, and 100 g of toluene and 100 g of ion-exchanged water were added to perform an extraction operation.
  • the upper layer-1 was separated, and extraction operation was performed again by adding 100 g of toluene and 100 g of ion-exchanged water to the lower layer.
  • the upper layer-2 was put in a 500 mL separatory funnel together with the upper layer-1 in particular, and 100 g of ion-exchanged water was added to perform a washing operation.
  • the obtained upper layer was separated and concentrated using an evaporator to obtain 22.8 g of a tan viscous liquid.
  • the yellow-brown viscous liquid was purified by column chromatography (silica gel, developing solvent: toluene) to obtain 9.0 g of a product (pale yellow solid). NMR and IR measurements were performed and it was confirmed that the obtained compound was 9,9-bis- (4-vinyloxyphenyl) fluorene represented by the following formula (purity 90.8%, yield 8.8). %).
  • FIG. 3 shows an IR chart of the obtained 9,9-bis- (4-vinyloxyphenyl) fluorene.
  • Comparative Example 2 Production of 9,9-bis- (4-vinyloxyphenyl) fluorene ⁇ 2> 9,9-bis (4-hydroxyphenyl) fluorene 49.5 g (0.14 mol), dimethyl sulfoxide in a 1 L SUS pressure vessel equipped with a stirrer, pressure gauge, gas introduction line, gas purge line and sampling line 450.7 g (5.76 mol) and potassium hydroxide 1.6 g (0.03 mol) were added, and the system was replaced with nitrogen gas while stirring at a rotational speed of 600 rpm. Subsequently, after the temperature of the reaction solution was set to 100 ° C., the inside of the system was replaced with acetylene gas, and maintained at 100 ° C. for 5 hours while maintaining the pressure at 0.04 MPa. Furthermore, it hold
  • 9,9-bis- (4-vinyloxyphenyl) fluorene is not assigned a CAS number and is not found in the literature as far as the present inventors know. It is believed that there is.
  • the polymerizable compound having the 9,9-bisphenylfluorene skeleton is resistant to heat. It is known to give a cured product excellent in optical characteristics, adhesion, etching resistance and the like.
  • 9,9-bis- (4-vinyloxyphenyl) fluorene obtained in the present invention is also used in resists, inks, paints, adhesives, raw materials for optical materials, etc., heat resistance, optical characteristics, adhesion, etching resistance, etc. It is useful as a raw material for an excellent polymerizable composition or as various synthetic reagents.

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Abstract

[Problème] Décrire un procédé pour produire un éther vinylique aromatique, qui peut résoudre les inconvénients des techniques conventionnelles et peut produire des éthers vinyliques aromatiques ayant différentes structures en utilisant un appareil simple sans utiliser un catalyseur coûteux. [Solution] La présente invention concerne un procédé pour produire un éther vinylique aromatique qui est caractérisé en ce qu'il comprend le chauffage d'un éther vinylique aromatique (1) qui a une structure telle qu'un atome d'hydrogène dans un groupe hydroxy phénolique est substitué par un groupe vinyloxyéthyle et est représenté par la formule (1) (dans laquelle R représente un résidu d'un phénol ayant n groupes hydroxy phénoliques ; et n représente un entier de 1 à 3) sans aucun solvant ou dans un solvant polaire aprotique en présence d'un composé de métal alcalin de manière à convertir l'éther vinylique aromatique (1) dans un éther vinylique aromatique (2) qui a une structure telle qu'un atome d'hydrogène dans un groupe hydroxy phénolique est substitué par un groupe vinyle et est représenté par la formule (2) (dans laquelle R et n sont tels que définis ci-dessus).
PCT/JP2012/004601 2011-07-29 2012-07-19 Procédé pour produire de l'éther vinylique aromatique Ceased WO2013018302A1 (fr)

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WO2014157676A1 (fr) * 2013-03-29 2014-10-02 東京応化工業株式会社 Composé fluorène contenant un groupe vinyle
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