WO2007139191A1 - 新規な多核体ポリ(ホルミルフェノール)類の製造方法 - Google Patents
新規な多核体ポリ(ホルミルフェノール)類の製造方法 Download PDFInfo
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- WO2007139191A1 WO2007139191A1 PCT/JP2007/061107 JP2007061107W WO2007139191A1 WO 2007139191 A1 WO2007139191 A1 WO 2007139191A1 JP 2007061107 W JP2007061107 W JP 2007061107W WO 2007139191 A1 WO2007139191 A1 WO 2007139191A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
- C07C47/57—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/562—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with nitrogen as the only hetero atom
- C07C45/565—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with nitrogen as the only hetero atom by reaction with hexamethylene-tetramine
Definitions
- the present invention relates to a process for producing polynuclear poly (formylphenol) s industrially easily and with high purity, and more specifically, polynuclear poly (hydroxymethyl) easily obtained from polynuclear polyphenols. Phenols) or polynuclear poly (alkoxymethylphenol) s as raw materials, reacted with hexamethylenetetramine in the presence of acid, and then hydrolysis of the reaction product makes it easy to industrially
- the present invention relates to a method for producing high purity with high yield.
- J. Chem. So, Perkin Trans. (1978, 318-321) discloses a method of reacting phenol with an equal amount of alkylmagnesium bromide and then reacting with formaldehyde to produce hololemy. This method has the disadvantage of using a large amount of expensive alkyl magnesium bromide.
- J. Chem. Soc, Perkin Trans. (1978, 1862-1865) discloses a method in which phenol is reacted with tin tetrachloride and then reacted with formaldehyde to formylate.
- industrialization is not preferable because it requires a large amount of wastewater treatment after the reaction.
- the ability of synthesizing salicylaldehydes with tin chloride using 2-hydroxybenzyl alcohol The present inventors have examined it, and it cannot be applied to polynuclear polyphenols.
- Japanese Patent Application Laid-Open No. 52-136141 discloses hydroxymethylphenols by oxidation to hydroxy. It describes a method for producing dimethylbenzaldehydes, and it is a gas-liquid reaction. Therefore, the reaction yield varies depending on the stirring state, etc., and pure oxygen is used, which makes industrialization difficult. .
- JP-A-5-125032 describes a method for tetraformylation of bisphenols.
- the power yield is low, and a larger amount of hexamethylenetetramine and acid are used than bisphenols. It is not an industrially feasible method with poor volumetric efficiency.
- WO2004 / 050231 discloses that 5-methyl 3-tertbutylbutyl acyldehydride and 1,3,5-triethynylbenzene are reacted in the presence of bis (triphenylphosphine) palladium, copper iodide and triethylamine. 1,3,5-tris [(5-tert-butyl 3-forminole 4-hydroxyphenyl) ethyl] benzene is described, but expensive raw materials are used.
- Patent Document 1 Japanese Patent Application Laid-Open No. 52-136141
- Patent Document 2 Japanese Patent Laid-Open No. 5-125032
- Patent document 3 W2004Z050231 gazette
- Non-Patent Document 1 J. Chem. Soc, Perkin Trans. (1978 318-321, 1862-1865)
- Non-Patent Document 2 Chungnam University Institute of Industrial Technology Research Papers No.4-2 (1977) Invention Disclosure of
- the present invention relates to a method for producing polynuclear formylphenols industrially easily with high yield and high purity. Specifically, polynuclear poly (hydride) easily obtained from polynuclear polyphenols. It is an object of the present invention to provide a method for producing a raw material from (roxymethylphenol) or polynuclear poly (alkoxymethylphenol).
- polynuclear polyphenols having bisphenols or polynuclear polyphenols having 3 or more hydroxy-substituted phenolic nuclei in the present invention. Hydroxymethyl-substituted or alkoxymethyl-substituted bisphenols that can be easily obtained by chemical conversion, etc., and polynuclear poly (hydroxymethylphenol) s or polynuclear poly (alkoxymethylphenols) are directly used as raw materials in the presence of acids.
- the polynuclear polyphenol represented by the general formula (1) is reacted with hexamethylenetetramine in the presence of an acid, and the reaction product is hydrolyzed in the next step.
- a process for producing polynuclear poly (formylphenol) represented by the general formula (2) is provided.
- R represents the same or different hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, an aliphatic hydrocarbon group which may have an ether group, R, R, R is the same
- 1 2 3 represents a hydrocarbon group, oxygen-containing atom hydrocarbon group, hydroxyl group, halogen group, halogenated hydrocarbon group which may be one or different, and a and c are 0 or an integer of 1 to 3
- B represents an integer of 0 or 1 to 2
- 1, n represents an integer of 1 to 3
- m represents an integer of 0 or:!
- X represents a linking group or a single bond
- Y represents a divalent alkylene group.
- the polynuclear polyphenols represented by the general formula (1) when m is 0, is a divalent linking group or a single bond and 1 + n is 2, the polynuclear polyphenols are Bisphenols represented by the general formula (3), multi-poly (formylphenol) compounds S represented by the general formula (2), and bis (formula (4) A method for producing polynuclear poly (formylphenol) s that are formylphenols) is a preferred embodiment of the present invention.
- R represents a hydrogen atom which may be the same or different, or an aromatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group, and n is 0 or: ! ⁇ 3 represents an integer, R may be the same or different hydrocarbon group, oxygen-containing hydrocarbon
- the bisphenol represented by the general formula (3) is a bis (hydroxymethylphenol) compound S represented by the general formula (6) when R is a hydrogen atom.
- a method for producing polynuclear poly (formylphenol), which is obtained by reacting bisphenols represented by the general formula (5) with formaldehyde in the presence of an alkali catalyst, is a preferred embodiment of the present invention. .
- R, n and X are the same as those in the general formula (3), and in the o-position and p-position of the hydroxyl group.
- At least one is unsubstituted.
- R, n and X are the same as those in the general formula (3), and the substitution position of the hydroxymethyl group
- R represents an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- m represents 0 or an integer of 2 to 2, provided that when m is 0, X is a trivalent to hexavalent valence. 1 + n is 3 to 6, and the polynuclear polyphenols are polynuclear polyphenols represented by the following general formula (8), and are polynuclear poly (formylphenols) represented by the above general formula (2).
- the production method of polynuclear poly (formylphenol), which is a polynuclear poly (formylphenol) represented by the following general formula (9), is another preferred embodiment of the present invention.
- R represents the same or different hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, an aliphatic hydrocarbon group which may have an ether group, R, R, R is the same
- 1 2 3 represents a hydrocarbon group, oxygen-containing atom hydrocarbon group, hydroxyl group, halogen group, halogenated hydrocarbon group which may be one or different, and a and c are 0 or an integer of 1 to 3
- B represents an integer of 0 or 1 to 2
- 1, n represents an integer of 1 to 3
- m represents an integer of 0 or:!
- X represents a linking group or a single bond
- Y represents a divalent alkylene group, provided that when m is 0, X represents a trivalent to hexavalent linking group and 1 + n represents 3 to 6.
- a process for producing a polynuclear poly (formylphenol) according to claim 1, which is obtained by reacting a polynuclear phenol represented by the following general formula (10) with formaldehyde in the presence of an alkali catalyst. are preferred embodiments of the present invention.
- ⁇ _ or ⁇ -position of the hydroxyl group is unsubstituted.
- X is a trivalent to hexavalent linking group and 1 + n is 3 to 6.
- substitution position of the hydroxymethyl group is ⁇ -position or ⁇ -position with respect to the hydroxyl group.
- X is a trivalent to hexavalent linking group and 1 + n is 3 to 6.
- the polynuclear polyphenols represented by the general formula (8) are polynuclear polyphenols in which R is an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- (Alkoxymethylphenol) analog S, the above general formula (11) obtained by reacting polynuclear polyphenols represented by the above general formula (10) with formaldehyde in the presence of an alkali catalyst The polynuclear poly (formylphenol) according to claim 1, which is obtained by further reacting the polynuclear poly (hydroxymethylphenol) represented by the formula (12) with an alcohol of the following general formula (12) in the presence of an acid catalyst.
- the production method is a preferred embodiment of the present invention.
- R represents an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- the polynuclear poly (formylphenol) as the target compound is represented by the above general formula (2), wherein R, R and R are the same or different.
- a hydrocarbon group, an oxygen-containing atom hydrocarbon group, a hydroxyl group, a halogen group, and a halogenated hydrocarbon group are shown, and a hydrocarbon group is preferred.
- the linking group X is a single bond or a divalent to hexavalent linking group.
- the linking group Y is a divalent anoalkylene group.
- a and c (indicated by n in the general formulas 3 to 6) are 0 or an integer of 1 to 3
- b is an integer of 0 or 1 to 2
- 1, n is 1
- m represents an integer of 0 or:! ⁇ 2.
- polynuclear poly (formylphenol) s are bis (formylphenol) s
- polynuclear poly (formylphenol) s have 3 or more hydroxy-substituted phenyl nuclei in the skeletal structure. It has polynuclear poly (formylphenol) s.
- the target compound is a polynuclear poly (formylphenol) compound represented by the above general formula (2), wherein m is 0, and X is a divalent
- polynuclear poly (formylphenol) s are represented by bis (formylphenol) s represented by the above general formula (4).
- X is a divalent linking group or a single bond
- the divalent linking group includes a bis (formylphenol) having a linking group to which the production method of the present invention can be applied.
- a hydrocarbon group, an oxygen-containing atom group, a sulfur-containing atom group, a nitrogen-containing atom group, a halogen-containing atom group, etc., and the hydrocarbon group may be a linear or branched chain which may have a substituent. Examples thereof include saturated to unsaturated hydrocarbon groups, polycyclic to monocyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic hydrocarbon groups.
- divalent hydrocarbon group examples include, for example, methylene, ethylene, propylene, 2,2-propylidene, having:! -30, preferably:!-15. 1,1-propylidene, 2,2-butylidene, hexamethylene, divalent acyclic saturated hydrocarbon groups exemplified by alkylene groups or alkylidene groups such as n-dodecylene, vinylene, 1,2-ethynesyl, pro Penylene, 2, 4_hexagen _ 1, 6-ylene, 2_butenylene, 2-methylene 1, 1, 3-propanediyl and the like, divalent acyclic unsaturated hydrocarbon group, 3 carbon atoms To: 15, preferably 5 to: 10, such as cyclopentylidene, cyclohexylidene, 1,4-cyclohexylene, 1,2-cyclohexenylene, 2,4-cyclohexagen 1_ylidene, etc.
- a divalent monocyclic alicyclic hydrocarbon group Divalent monocyclic aromatic hydrocarbon groups exemplified by phenyl groups such as P-phenylene, 2-propyl-1,4-phenylene, 2,3-indenylidene, 1,2-naphthylene, 2,7-phenanthrylene 9, 9 Fluorenylidene etc.
- Divalent condensed polycyclic hydrocarbon group bicyclo [2.2.1] heptane 2,3 diyl, 6-ethylbicyclo [2.2.1] heptane 1,2,3 diyl, tetracyclo [4.4.0.1 2 '5 .1 "° ] dodec emissions 3,4 Jiiru, Adamantan 1, divalent bridged cyclic hydrocarbon group exemplified by 3-Jiiru like, spiro [3.4] octane-7, 8 Divalent spiro hydrocarbon group exemplified by diyl, etc., 1, 1'-biphenyl-1,4,4 'diyl, P-terphenyl-1,4 "-dinole, 1,1'-diphenylmethane 4,4' Dizyl, stilbene 4, 4 'dil and the like, bivalent polycyclic aggregate hydrocarbon groups, 2_pinene-10-ylidene,
- Examples include terpene hydrocarbon groups exemplified by 5_norbornene_2,3_diyl and the like.
- Examples of the substituent that the divalent hydrocarbon group may have include a divalent substituent or a monovalent substituent that can act as a linking group.
- a monovalent hydrocarbon group or a monovalent hydrocarbon group corresponding to the divalent hydrocarbon group for example, a monovalent acyclic saturated hydrocarbon group, acyclic unsaturated hydrocarbon group, monocyclic fat Ring hydrocarbon group, monocyclic fragrance Group hydrocarbon group, condensed polycyclic hydrocarbon group, bridged ring hydrocarbon group, polycyclic aggregate hydrocarbon group, spiro hydrocarbon group, terpene hydrocarbon group, etc., specifically, for example, carbon atom
- monovalent acyclic unsaturated hydrocarbon group carbon
- Monovalent monocyclic such as cyclopentyl, cyclohexyl, cyclohexene mono 1-inole, cyclohexa-2,5_gen _ 1-yl having 3 to 15, preferably 5 to 10 atoms
- phenyl groups such as alicyclic hydrocarbon groups, phenylol, 2-propyl monophenyl, etc.
- hydrocarbon group having the above substituent examples include methylethylmethylene, methylisobutylmethylene, cyclohexylmethylmethylene, dicyclohexylmethylene, diphenylmethylene, phenylmethylene and biphenylmethylene.
- examples of the substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom include, for example, alkoxy groups such as monovalent methoxy, ethoxy, and cyclohexyloxy, allyloxy groups such as phenoxy, 4 —Substituents containing ether groups such as methoxyphenyl group, 2-methoxyphenyl group, furyl group, substituents containing carbonyl group such as acetyl group such as acetyl, propionyl, butyrylbenzoyl, allyloyloxy, methacryloyloxy , Substituents containing primary, secondary or tertiary ester groups such as acyloxy groups such as acetoxy, t-butoxy and benzoyloxy, hydroxyl groups or 4-hydroxyphenyl, 4-hydroxyphenylmethyl, 3-hydroxy _n— Butyl, 2-hydroxyethyloxy
- Examples thereof include a monovalent amino group, a divalent ether group, a carbonyl group, an ester group, an amide group, an imino group, and a sulfide group.
- the divalent hydrocarbon group having a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom specifically, for example, a di (trifluoromethyl) methylene group And substituted methylene groups such as 4-hydroxy_3-methoxyphenylmethylene group (Chemical Formula 1) and the like, and for example, the following formula 2 having two methylene groups at both ends of the hydroxyphenylene group: Group, other thiophene-2_yl, furan_2_yl, quinoline-2-yl, 2H-pyran-2-yl, 1,4-dihydro-1-4-pyridyl, etc. Etc.
- divalent linking group when the linking group X is an oxygen-containing atom group, a sulfur-containing atom group, a nitrogen-containing atom group, or a halogen-containing atom group include, for example, carbonyl Group, ethereol group, oxocarbonyl group (carboxylate group), sulfide group, sulfoxide group, sulfone group, thioketone group, thiocarbonyl group, carbonyldioxy group, sulfonyldioxy group, azo group, hydrazo group,
- a divalent hetero compound group exemplified by an imino group, a ureylene group, or the like, or a hydroxyphenyl group of the following general formulas (3) and (4) is bonded via a hydrocarbon group.
- Bonding group X as a whole is preferably a saturated hydrocarbon group, a hydrocarbon group containing an unsaturated bond of only an aromatic hydrocarbon group, a saturated hydrocarbon group containing a primary or secondary ester group, or a saturated hydrocarbon group containing an ether group.
- Hydrogen groups (excluding 1,2_epoxides, 1,3_epoxides, and acetal groups) are preferred, and particularly preferred are saturated hydrocarbon groups and hydrocarbon groups containing only unsaturated hydrocarbon aromatic bonds. .
- R represents the same or different hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, or an aliphatic hydrocarbon group which may have an ether group, and n is 0 or :! Represents an integer of 3 to 3, R may be the same or different hydrocarbon group, oxygen-containing atom hydrocarbon
- n and X are the same as those in general formula 3.
- R is a hydrocarbon group
- R when R is a hydrocarbon group, the above-described linking group X may be substituted.
- the hydrocarbon group a linear or branched saturated or unsaturated hydrocarbon group which may have a substituent, a polycyclic to monocyclic aliphatic group Examples thereof include a cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic hydrocarbon group.
- monovalent hydrocarbon group examples include, for example, methinole, ethyl, isopropylinole, tert-butyl, sec having carbon atoms of:! ⁇ 30, preferably:! ⁇ 15.
- Monovalent polycyclic aggregate hydrocarbons exemplified by monovalent spirohydrocarbon groups, 1, 1'-biphenylenole 4-inore, P-terfeninole 4-inore, 1,1'-diphenylenomethan-4-yl, stilbene 4-yl, etc.
- a hydrogen group etc. are mentioned.
- the substituent that may be substituted with these monovalent hydrocarbon groups is the same as the monovalent hydrocarbon group that may be substituted with the divalent hydrocarbon group of the bonding group X.
- the oxygen-containing hydrocarbon group is a hydrocarbon group in which one or more oxygen atoms are bonded in the chemical structure.
- an alkoxy group such as methoxy, ethoxy, cyclohexyloxy, phenoxy, etc.
- Substituents containing ether groups such as aryloxy groups, 4-methoxyphenyl groups, 2-methoxyphenyl groups, furyl groups, etc.
- substituents containing carbonyl groups such as acetyl groups such as acetyl, propionyl, butyrylbenzoyl, and allyloyl
- halogenated hydrocarbon group examples include trifluoromethyl, 3_bromo_n-propyl, and the like.
- R is a halogen group, specifically, for example, a chlorine atom, a bromine atom, a fluorine atom
- Preferred R is a carbon atom number:! To 20 and an oxygen atom number of 0 to 2, particularly preferably
- R force Carbohydrate having a hydroxyl group, ether group, halogen group (bromine, chlorine, etc.) at the first position
- the substitution position of the formyl group is preferably the onoleso position or the para position with respect to the hydroxyl group.
- Compounds represented by formulas (13) and (14) are preferred.
- n, R, and X are the same as those in general formula 3.
- n, R, and X are the same as those in general formula 3.
- the bisphenol represented by the general formula (3) is reacted with hexamethylenetetramine in the presence of an acid, and then the reaction product is hydrolyzed, thereby starting material.
- R represents the same or different hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, or an aliphatic hydrocarbon group which may have an ether group, and n is 0 or :! Represents an integer of 3 to 3, R may be the same or different hydrocarbon group, oxygen-containing atom hydrocarbon
- X represents a divalent linking group or a single bond.
- R represents a hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, or an ether group.
- Represents an aliphatic hydrocarbon group that may have, X, R, and n are represented by the general formula (4)
- X, R, and n are specifically defined in the general formula (4) above.
- X, R, and n may be the same or different.
- R represents a hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group or an ether group, which may be an aliphatic hydrocarbon group, and has an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- the aliphatic hydrocarbon group which may be used include an alkyl group, an alkoxyalkyl group, a phenylalkyl group, etc., which are preferably substituted or unsubstituted saturated aliphatic hydrocarbon groups, and further, primary or 2 Preferred are substituted or unsubstituted alkyl groups.
- the alkyl group is, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched chain having 1 to 10 carbon atoms such as a methyl group, an isopropyl group, or an n-butyl group.
- the bonding group X is preferably one in which both hydroxyphenyl groups are bonded on the same carbon of the bonding group X.
- the bonding group X is preferably one in which both hydroxyphenyl groups are bonded on the same carbon of the bonding group X.
- the following general formulas (15), (16) And compounds as shown in FIG. The use of bisphenol having such a chemical structure as a raw material is preferable because it has an effect of increasing the yield as compared with the Duf f reaction. [0050] [Chemical 22]
- R is the same as that in the general formula (3), and R ', R' and R are each independently hydrogen.
- R and R are divalent hydrocarbons of the linking group X in general formula (3)
- R and R are each independently a hydrogen atom, an alkyl group having from 10 to 10 carbon atoms,
- 5 to 10 carbon atoms an alicyclic or bridged alkylidene group having 5 to 20 carbon atoms in which a cycloalkyl group having 10 carbon atoms or a ring containing carbon atoms of a bonding group is formed.
- Bisphenols which are the corresponding raw materials of the compound of formula (16), have an alkyl group at R ′
- R which is the direct raw material of the present invention, is obtained by reacting 0-alkylphenols, which are raw material phenols, with formaldehyde in the presence of an alkali catalyst and removing 4,4'-methylenebisphenol from the reactor. Since bis (hydroxymethylphenol) s represented by the general formula (15) can be obtained, it is preferable.
- the reaction formula is shown below.
- R represents an alkyl group, and R and R represent a hydrogen atom or an alkyl group.
- the target compound is a polynuclear poly (formylphenol) compound represented by the general formula (2) wherein m represents 0 or an integer of 1 to 2. However, when m is 0, X is a trivalent to hexavalent linking group, and 1+ n is 3 to 6.
- Polynuclear poly (formylphenol) s are polynuclear poly (polynuclear poly (polynuclear) having three or more hydroxy-substituted vinyl nuclei ( Formylphenol) and represented by the above general formula (8).
- X represents a single bond or a bivalent to hexavalent linking group, provided that when m is 0, X represents a trivalent to hexavalent linking group.
- X is preferably a divalent to tetravalent linking group.
- the divalent to hexavalent linking group is not particularly limited as long as it is a polynuclear poly (formylphenol) having a linking group to which the production method of the present invention can be applied.
- a hydrocarbon group, oxygen-containing atomic group, A sulfur atom group, a nitrogen-containing atom group, a halogen-containing atom group, etc., and the divalent to hexavalent hydrocarbon group optionally has a substituent, preferably a straight chain or 1 to 30 carbon atoms.
- Branched saturated or unsaturated hydrocarbon group polycyclic or monocyclic alicyclic hydrocarbon group, aromatic hydrocarbon group or condensed polycyclic hydrocarbon group such as 9, 9 fluorenylidene, adamantane 2, 3 Bridged ring hydrocarbon groups such as dill, spiro [3.4] Octo 7, 8—spiro hydrocarbon groups such as dill, polycyclic aggregate hydrocarbon groups such as P-terphenyl 1, 4 "_ dill, 5— Terpene hydrocarbon groups such as norbornene-2,3-diyl, complex such as 2,5-thiophenzyl Examples thereof include a cyclic hydrocarbon group.
- the divalent to hexavalent hydrocarbon group may have a divalent substituent that can act as a linking group or a monovalent substituent.
- X include, for example, a trivalent saturated or unsaturated hydrocarbon group, a methine group (a chemical formula 3), and an ethyridine group (a chemical formula represented by the following chemical formula). 4), cyclohexane 1 , 1, 4 Tolyl group (Chemical formula 5), Propyridine group (Chemical formula 6), Propane 1, 2, 3 Trinole group, Butane 1, 3, 3-tolyl group (Chemical formula 7 ), 1, 4, 4-cyclohexane-1-ene tolyl group (chemical formula 8),
- a tetravalent saturated or unsaturated hydrocarbon group represented by the following chemical formula: ethane 1, 1
- Examples include aromatic hydrocarbon groups represented by the following chemical formula.
- the divalent to hexavalent linking group when the linking group X is an oxygen-containing atom group, a sulfur-containing atom group, a nitrogen-containing atom group, or a halogen-containing atom group specifically, for example, , Ketone group, ether group, oxocarbonyl group (carboxylate group), sulfide group, sulfoxide group, snophone group, thioketone group, thiocarbonyl group, carbonyldioxy group, sulfonyldioxy group, azo group , Hydrazo group, imino group, ureylene group, hydrocarbon having halogen atom group It is possible to enumerate a chain or cyclic compound group having a bi- to hexa-valent hetero atom exemplified by an elementary group.
- Y represents a divalent alkylene group, preferably a linear or branched saturated hydrocarbon group having 1 to 5 carbon atoms.
- a halogen group and a halogenated hydrocarbon group, a and c each represent 0 or an integer from! To 3; b represents 0 or an integer from 1 to 2;
- the hydrocarbon group may have a monovalent linear or branched saturated or unsaturated hydrocarbon group, polycyclic to monocyclic alicyclic hydrocarbon group, aromatic carbon which may have a substituent. Examples thereof include a hydrogen group and a heterocyclic hydrocarbon group.
- the monovalent hydrocarbon group include, for example, methinole, ethyl, isopropylinole, t-butyl, sec-butyl having:! -30, preferably:!-15. , Isobutyl, t-year-old octyl, monovalent acyclic saturated hydrocarbon group exemplified by alkyl groups such as n-dodecyl, bur, allyl, hexane 2, 4-gen 1yl, butter 2-en 1 A monovalent acyclic unsaturated hydrocarbon group exemplified by yl, etc., having 3 to 15 carbon atoms, preferably 5 to 7, cyclopentyl, cyclohexyl, 2 cyclohexyl 3yl, cyclohexa Monovalent monocyclic alicyclic hydrocarbon groups exemplified by 2,5-gen 1-yl, etc., monovalent monocyclic aromatic hydrocarbon groups exemplified by
- the oxygen-containing atom hydrocarbon group is a hydrocarbon group in which one or more oxygen atoms are bonded in the chemical structure. Specifically, for example, an alkoxy group such as methoxy, ethoxy, cyclohexyloxy, phenoxy, etc.
- Substituents containing ether groups such as aryloxy group, 4-methoxyphenyl group, 2-methoxyphenyl group, furyl group, etc., substituents containing carbonyl group such as acetyl group, propionyl, butyrylbenzoyl, etc., and allyloyl
- substituents containing primary, secondary or tertiary ester groups such as oxy, methacryloyloxy, acetoxy, benzoyloxy, etc., 4-hydroxyphenyl, 4-hydroxyphenylmethyl, 3-hydroxy_n—
- Substituents containing hydroxyl groups such as butyl and 2-hydroxyethyloxy, furan _ 2_yl, 2H-pyran-2 Monovalent heterocyclic hydrocarbon group exemplified by Le, and the like.
- halogen group examples include a chlorine atom, a bromine atom, and a fluorine atom.
- halogenated hydrocarbon group examples include a halogenated alkyl group such as a trifluoromethyl group.
- R, R and R are those having carbon atoms:! -20 and oxygen atoms 0-2, especially
- alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 5 to 10 carbon atoms.
- 1, n represents an integer of 1 to 3
- m represents 0 or an integer of 1 to 2, provided that when m is 0, 1 + n is 3 to 6.
- Preferred 1, n and m are such that m is 0 and 1 + n is 3 or 4, m is 1 and 1 and n are both 1.
- the substituents R and R are the same, and the substitution force for the OH group is the same.
- the ⁇ H group is in the 4-position relative to the bond position of the linking group X on the phenyl nucleus.
- the ⁇ H group is bonded to the phenyl nucleus. It is preferably in the 2-position relative to the bonding position of the combined groups X and Y.
- the substitution position of the formyl group is preferably an ortho position or a para position with respect to the hydroxyl group.
- Examples thereof include compounds represented by the following general formulas (17), (18), and (19).
- X is a divalent linking group, R, R, R force S methyl groups a , b and
- polynuclear poly (formylphenol) s represented by the above general formula (9) specific compounds include, for example, 1--methyl- ⁇ - (3-forminolay 5-methyl-4-hydroxyphenyl) ethyl] — 4— [a, —bis (3-forminolyl 5-methyl 4-hydroxyphenyl) ethyl] benzene and the like.
- the polynuclear polyphenols represented by the general formula (8) are converted to acid.
- the polynuclear poly (formylphenol) compound represented by the general formula (9) which is the target product corresponding to the raw material, is obtained. Can be manufactured.
- R represents the same or different hydrogen atom or an aromatic hydrocarbon group, a hydroxyl group, an aliphatic hydrocarbon group which may have an ether group, R, R, R is the same
- 1 2 3 represents a hydrocarbon group, oxygen-containing atom hydrocarbon group, hydroxyl group, halogen group, halogenated hydrocarbon group which may be one or different, and a and c are 0 or an integer of 1 to 3
- B represents an integer of 0 or 1 to 2
- 1, n represents an integer of 1 to 3
- m represents an integer of 0 or:!
- X represents a linking group or a single bond
- Y represents a divalent alkylene group, provided that when m is 0, X represents a trivalent to hexavalent linking group and 1 + n represents 3 to 6.
- the polynuclear poly (formylphenol) compound represented by the general formula (9) which is the target product is obtained by converting the polynuclear polyphenol represented by the general formula (8) of the corresponding raw material into an acid. It is produced by reacting with hexamethylenetetramine in the presence of water and hydrolyzing the reaction product in the next step. By this reaction, the hydroxymethyl group or alkoxymethyl group in the polynuclear polyphenol compound represented by the above general formula (8), which is the raw material compound, is converted to a formyl group, and the target compound is represented by the general formula (9). A polynuclear poly (formylphenol) compound is obtained.
- R, R, and R may be the same or different hydrocarbon groups and oxygen-containing atomic carbons
- a hydrogenated group, a hydroxyl group, a halogen group, a halogenated hydrocarbon group, a and c are 0 or: represents an integer of! To 3, b is an integer of 0 or 1 to 2, 1, n is 1 to Represents an integer of 3, m represents an integer of 0 or:! To 2, X represents a bonding group or a single bond, Y represents a divalent alkylene group, R represents a hydrogen atom or an aromatic hydrocarbon group, An aliphatic hydrocarbon group which may have a hydroxyl group or an ether group, provided that when m is 0, 1 + n represents 3-6.
- R, R, R and a, b, c and 1, m, n and X, Y are specifically represented by the general formula (9).
- n and m are such that m is 0 and 1 + n is 3 or 4, m is 1 and 1 and n are both 1.
- substituents R, R and R are the same, and the ⁇ H group
- the substitution position for is the same.
- the OH group is preferably in the 4-position relative to the bonding position of the bonding group X on the phenyl nucleus.
- the OH group is a bonding group on the phenyl nucleus. It is preferably in the 2nd position relative to the X and Y bond positions.
- R is the same as that of the general formula (3).
- the substitution position of the hydroxymethylol group or alkoxymethyl group is preferably the onoleso position or the para position of the hydroxyl group.
- the other cases where there are substituents at the o-position and p-position are more preferred because they can be synthesized with good yield.
- at least R, R and R in the general formula (8) are more preferred because they can be synthesized with good yield.
- one is a hydrocarbon group having a hydroxyl group, an ether group or a halogen group (bromine, chlorine, etc.) in the ⁇ -position, particularly a hydroxymethyl group or an alkoxymethyl group.
- Examples of the polynuclear polyphenols represented by the general formula (8) include compounds represented by the following general formulas (20), (21) and (22).
- R represents a hydrogen atom or an aliphatic hydrocarbon group which may have a hydrogen atom, an aromatic hydrocarbon group, a hydroxyl group or an ether group, and has an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- the aliphatic hydrocarbon group which may be used include an alkyl group, an alkoxyalkyl group, a phenylalkyl group, etc., which are preferably substituted or unsubstituted saturated aliphatic hydrocarbon groups, and further, primary or 2 Preferred are substituted or unsubstituted alkyl groups.
- the alkyl group is, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. It is an alkyl group. Specifically, for example, methinole, ethyl, cyclohexyl and the like can be mentioned.
- polynuclear hydroxymethylphenols or polynuclear alkoxymethylphenols represented by the general formula (8) that are the raw materials in the production method of the present invention include, for example, specific compounds such as ,
- the Duff reaction which is conventionally known as a method for introducing a formyl group into an aromatic ring, is a reaction in which an unsubstituted benzene ring is directly formylated, whereas an aromatic It is possible to formylate a hydroxymethyl group or an alkoxymethyl group bonded to a family ring. The mechanism of this reaction is unknown. It is speculated that some Schiff base-like base is formed as an intermediate and is hydrolyzed to formylate it.
- the production method of the present invention is obtained by reacting, for example, 4,4'-methylenebis (2-methyl-6hydroxymethylphenol) with hexamethylenetetramine in the presence of an acid in a reaction formula.
- the following reaction formula (2) shows a case where 4,4′-methylenebis (2-methyl-6formylphenol) is obtained by hydrolyzing the obtained reaction product.
- reaction formula (2) [0086] Further, for example, 1--methyl- ⁇ (3 hydroxymethyl-5-methyl-4-hydroxyphenyl) ethyl] —4 -— [ ⁇ , ⁇ -bis (3-hydroxymethyl-1-5-methyl-4-hydroxyphenyl) ethyl] After reacting with hexamethylenetetramine in the presence of an acid from benzene (Chemical Formula 15), the resulting reaction product is hydrolyzed to give 1_ [Hydroxymethyl- (3-formyl).
- polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by the general formula (1) is converted to hexamethylenetetramine in the presence of an acid.
- the acids used include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic sulfonic acids such as ⁇ toluenesulfonic acid, silica-alumina solid catalysts such as white clay, acidic clay and zeolite, tin chloride.
- Lewis acids such as iron chloride and boron fluoride, aliphatic and aromatic organic carboxylic acids such as acetic acid, formic acid, succinic acid and benzoic acid, or trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, monofluoroacetic acid, and monochloroacetic acid And halogenated organic carboxylic acids such as fluorobenzoic acid and inorganic weak acids such as boric acid.
- Lewis acids such as iron chloride and boron fluoride, aliphatic and aromatic organic carboxylic acids such as acetic acid, formic acid, succinic acid and benzoic acid, or trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, monofluoroacetic acid, and monochloroacetic acid
- halogenated organic carboxylic acids such as fluorobenzoic acid and inorganic weak acids such as boric acid.
- liquid halogenated organic carboxylic acids are particularly preferred, with organic carboxylic acids and boric acids being preferred.
- the amount of acid used in the reaction depends on the type of acid, the range of the amount added, or the optimum amount of acid varies.
- polynuclear poly (hydroxymethylphenol) s or polynuclears are used.
- the poly (alkoxymethylphenol) s are in a range of about 0 ⁇ :! to 100 mol times, preferably about 1 to 50 mol times, per mol of poly (alkoxymethylphenol) s.
- 1 mol of the bisphenol The range is from! To 30 mole times, preferably from 5 to 20 mole times.
- polynuclear poly (hydroxymethylphenol) s represented by the general formula (1) or the polynuclear poly (alkoxymethylphenols) represented by the above general formula (8) has three or more hydroxy-substituted phenols.
- (l + m + n) X 0. per mol of polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) s. It is in the range of 5 mol times to (1 + m + n) X 15 mol times, preferably in the range of (l + m + n) X 2.5 mol times to (1 + m + n) X 10 mol times. .
- (1 + m + n) is 3
- it is preferably in the range of 7.5 to 30 mole times
- (1 + m + n) is 4, preferably 10 mole times. It is in the range of ⁇ 40 mole times.
- hexamethylenetetramine is not limited, for example, hexamethylenetetramine produced by adding ammonia and formaldehyde, which are raw materials of hexamethylenetetramine, to the reaction system.
- the amount of hexamethylenetetramine is the sum of 1 + m + n per mol of polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by the above general formula (1) If the number of moles is greater than or equal to the number of moles, there is no particular limitation, but if it is excessive, the volumetric efficiency decreases, so it is usually in the range of 10 moles or less, preferably (1 + m + n) X 1. The range is from 05 mol times to (1 + m + n) XI .5 mol times.
- the polynuclear poly (hydroxymethylphenol) or the polynuclear poly (alkoxymethylphenol) is a bisphenol represented by the above general formula (3)
- volume efficiency decreases when it is excessive, so usually it is in the range of 2 to: 10 mol times, preferably in the range of 2 to 5 mol times, more preferably 2 .:! ⁇ 3 mole times range.
- polynuclear poly (hydroxymethylphenol) s or polynuclear poly (alkoxymes) is a polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) having three or more hydroxy-substituted phenyl nuclei represented by the general formula (8).
- (1 + m + n) is 3, preferably in the range of 3.:! To 4.5 mole times, and when (1 + m + n) is 4, preferably 4.2-6 It is the range of mole times.
- a solvent may or may not be used. If the reaction raw material is dissolved and the reaction composition can be stirred, it is particularly necessary. However, if the acid used or the melting point of the raw material is high, stirring is difficult because the reaction solution has a high viscosity at the reaction temperature. It ’s better to use it.
- the solvent to be used is not particularly limited as long as it does not inhibit the reaction.
- chain or cyclic aliphatic ethers such as ether, jetyl ether and tetrahydrofuran, preferably ethyl acetate, n_butyl acetate and the like are preferable.
- C1-C4 lower aliphatic alcohols such as primary or secondary aliphatic esters, methanol, ethanol, butanol, etc., cycloaliphatic alkyl alcohols such as cyclohexanol, aromatics such as toluene, xylene, ethylbenzene, etc.
- Aromatic hydrocarbon is preferable.
- the method and order of the reaction raw materials are not limited, and the method and order may be appropriately selected according to the properties of the raw materials used.
- the polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by the general formula (1) as a raw material is added to a solution in which an acid, hexamethylenetetramine and a solvent may be present.
- the acid and hexamethylenetetramine may be added to a solution in which polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) and a solvent may be present.
- polynuclear poly (hydroxymethylphenol) s or polynuclear poly (alkoxymethylphenols), hexamethylenetetramine and a solvent may be present, or an acid may be added to the solution.
- an organic carboxylic acid is used as the acid
- the starting polynuclear poly (hydroxymethylphenol) s or polynuclear poly (alkoxymethylphenol) s are added to a solution containing the organic carboxylic acid and hexamethylenetetramine. I prefer the method.
- the reaction temperature and pressure are not particularly limited as long as the reaction can be carried out smoothly, but the reaction temperature is usually in the range of _50 to 150 ° C, preferably in the range of 0 to 110 ° C, more preferably The range is preferably 50 to 90 ° C.
- the reaction pressure is in the range of slightly reduced pressure to slightly increased pressure, preferably about normal pressure.
- polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by the above general formula (1) is hexanemethylene in the presence of an acid.
- the intermediate product obtained by reaction with tetramine is hydrolyzed to obtain the desired polynuclear poly (formylphenol) represented by the general formula (2).
- the reaction intermediate product obtained by reacting with hexamethylenetetramine may be separated by filtration or the like, or may be further purified as necessary. From the viewpoint of improving the efficiency and yield, it is preferable to use the reaction product mixture with hexamethylenetetramine as it is.
- a catalyst may or may not be used, but a catalyst is preferably used.
- an acid catalyst or an alkali catalyst is used.
- an acid catalyst is preferred because it is easily decomposed.
- the acid used in the reaction with hexamethylenetetramine may be used as it is as a hydrolysis catalyst. In this case, if the reaction is slow, an acid may be added.
- a known acid catalyst may be newly added and used. However, if a strong acid is used in an excessive amount, care should be taken because the formyl group and ester group are decomposed to lower the yield.
- the amount of the acid used is usually from 0.:! To 10 0 with respect to the polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by the general formula (1).
- the molar range is preferably in the range of about:! To 20 molar times.
- examples of the acid catalyst used for the hydrolysis include mineral acids such as hydrochloric acid and sulfuric acid, organic sulfones such as p-toluenesulfonic acid, and organic strength rubonic acids such as phosphoric acid or acetic acid, formic acid and trifluoroacetic acid.
- examples of the alkali catalyst used for the hydrolysis include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as tetramethylammonium hydroxide.
- the amount of water in the reaction composition is not particularly limited as long as the reaction can be carried out smoothly, but in terms of volumetric efficiency, the above general formula ( Usually, (1 + m + n) XI mole times to (1 + m + n) X 40 to the polynuclear poly (hydroxymethylphenol) or polynuclear poly (alkoxymethylphenol) represented by 1)
- the molar range is preferably in the range of (1 + m + n) ⁇ 10 molar times to (1 + m + n) ⁇ 25 molar times.
- the reaction temperature and pressure are in the range of 2 to 80 mol times, preferably in the range of 20 to 50 mol times, as long as the reaction can be performed smoothly, but the reaction temperature is usually
- the range is from _50 to 150 ° C, preferably from 0 to 100 ° C, more preferably from 50 to 80 ° C.
- the reaction pressure is in the range of slightly reduced pressure to slightly increased pressure, preferably about normal pressure.
- the target crude product or purified product can be obtained in good yield from the obtained reaction completed mixture according to a known method. For example, if the target product in the reaction mixture is precipitated as crystals, the target product may be filtered off as it is, or if not precipitated as crystals, a poor solvent is added to the reaction mixture to precipitate the target product. You can separate them.
- the acid catalyst in the reaction completion mixture is neutralized into the reaction completion mixture.
- the separation and precipitation of the target product for example, toluene, xylene, methyl isobutyl ketone, Separation and precipitation operations such as separation of the water layer and the oil layer containing the target product by adding a solvent that can be separated from water such as ether may be performed.
- the acid catalyst in the reaction mixture is not neutralized. After the target product is precipitated and separated, the obtained crude target product may be washed with water to remove the acid.
- the acid used in the reaction is a low-boiling acid such as trifluoroacetic acid
- the acid catalyst in the reaction mixture is not neutralized. It can be reused as it is.
- the crude product thus obtained can be separated from water such as toluene, xylene, methyl isobutyl ketone or ether for further purification of the target product. After the solvent is added and dissolved, the aqueous layer is separated and the oil layer is washed with water to obtain an oil layer containing the desired product.
- a crystallization solvent is added to the oil layer, and crystallization and filtration are performed to obtain crude crystals of the target product. If the purity of the crude crystals is low, the above recrystallization operation may be further performed once to several times as necessary.
- the polynuclear polyphenols represented by the general formula (1) used directly as a raw material are not particularly limited in the production method.
- the polynuclear poly (hydroxymethylphenol) represented by (1) or the polynuclear poly (alkoxymethylphenol) is a bis (phenol) represented by the above general formula (3), for example, It can be easily obtained from bisphenols represented by the following general formula (5) by a known hydroxymethylation reaction or alkoxymethylation reaction.
- reaction product examples include bis (hydroxymethylphenol) represented by the following general formula (6) when a hydrogen atom is added to the bisphenol represented by the general formula (3). ⁇ nol).
- bis (alkoxymethylphenol) s can be obtained by further converting the obtained bis (hydroxymethylphenol) s in the presence of an acid catalyst to the following general formula (7) It can manufacture easily by making it react with alcohol represented by these.
- the alcohol represented by the general formula (7) include methanol, n_butanol, methoxyethanol, and ethylene glycol, which are preferably primary or secondary alcohols.
- R represents an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- R represents an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- polynuclear poly (hydroxymethylphenol) s represented by the general formula (1) or the polynuclear poly (alkoxymethylphenol) s represented by the above general formula (8) may be 3 or more hydrides.
- (alkoxymethylphenol) s for example, it can be easily obtained from polynuclear polyphenols represented by the following general formula (10) by a known hydroxymethylation reaction or alkoxymethylation reaction. it can.
- reaction product examples include a polynuclear poly (hydroxy) represented by the following general formula (11) when R is a hydrogen atom in the polynuclear polyphenols represented by the general formula (8). (Methylphenol))
- polynuclear poly (hydroxymethylphenol) s can be easily prepared by known methods such as those described in JP-A-2003-92222, in which polynuclear polyphenols are reacted with formaldehyde in the presence of an alkali catalyst. Can be manufactured.
- polynuclear polyph The following is the case for 1- [H-methyl-1- ⁇ - (5-methyl 4-hydroxyphenyl) ethyl]-4-[ ⁇ , H-bis (5-methyl 4-hydroxyphenyl) ethyl] enol as the following: This is illustrated in reaction formula (6).
- polynuclear poly (alkoxymethylphenol) s can be produced, for example, by the following method using the polynuclear poly (hydroxymethylphenol) s obtained above in the presence of an acid catalyst. It can be easily produced by reacting with the alcohol represented by the general formula (12). Preferred alcohols and specific examples of the alcohol represented by the general formula (12) are the same as those in the general formula (7).
- Such a production method is, for example, a tri (hydroxymethyl) compound as a polynuclear poly (hydroxymethylphenol) obtained by the following reaction formula (6): 1--methyl- ⁇ - (3-hydroxymethyl mono-5- The case of methyl 4-hydroxyphenyl) ethyl] -4- [ ⁇ , ⁇ bis (3-hydroxymethyl-5-methyl-4-hydroxyphenyl) ethyl] benzene is exemplified in the following reaction formula (7).
- R is an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group. Indicates a hydrogen group.
- R represents an aliphatic hydrocarbon group which may have an aromatic hydrocarbon group, a hydroxyl group or an ether group.
- polynuclear polyphenol represented by the general formula (1) when used as a starting material, a polynuclear poly (hydroxymethylphenol) corresponding to the target compound is used, Alternatively, whether to use polynuclear poly (alkoxymethylphenol) should be determined as appropriate in consideration of the production method, the ease of purification, the stability of the compound, toxicity, reaction selectivity, etc. Can do.
- a polynuclear polyphenol represented by the general formula (1) is used as a raw material, reacted with hexamethylenetetramine in the presence of an acid, and then the reaction product is hydrolyzed.
- polynuclear formylphenols that are easy to implement, have a high yield, and have a high volumetric efficiency, and are useful as raw materials for resist materials, polymerization catalysts, resins, and the like.
- polynuclear poly (alkoxymethylphenol) s can be easily produced from the corresponding polynuclear polyphenols, which is consistently easy to implement industrially and highly from polynuclear polyphenols. It is possible to produce polynuclear poly (formylphenol) with high yield and high efficiency.
- the temperature was raised to 85 ° C., and further post-reaction was performed for 3 hours with stirring.
- a part of the obtained reaction finished solution was collected, hydrolyzed, and analyzed by HPLC.
- the composition value of the main component considered to be the target product was 70%.
- reaction completion liquid 800. Og of water was added to the obtained reaction completion liquid, and a hydrolysis reaction was performed at a temperature of 60 ° C for 1 hour. Crystals precipitated during this reaction. After completion of the reaction, the resulting reaction mixture was neutralized by adding 16% aqueous sodium hydroxide solution 1471. Og, and further adding 50 g of methyl isoptyl ketone and 50 g of methanol, followed by cooling and precipitation. The crystals were filtered to obtain 302.3 g of a crude product.
- the obtained crude product was charged into a 2 L four-necked flask, to which 369.2 g of methylisobutyl ketone and 255.6 g of Tonolene were calorie-free, maintained at a temperature of 70 ° C., and kept in a slurry state for 30 minutes. After stirring, the mixture was cooled, and the precipitated crystals were filtered and dried to obtain 196.8 g of yellow powder crystals having a purity of 95.8% by HPLC. The yield based on 4,4'-methylenebis (2-methyl-6-hydroxymethyl phenol) was 69.3%.
- the obtained crystal was confirmed to be the target product.
- the obtained crystal was confirmed to be the target product.
- Og and Tolenene 50. Og were added and maintained at a temperature of 80 ° C. for 1 hour (the solution was in a slurry state) After cooling, the precipitated crystals were filtered and dried to obtain 45.3 g of a yellow powder having a purity of 94.6% by HPLC.
- the obtained crystal was confirmed to be the target product.
- the composition value (area ratio) of the main component considered to be the target product was 60.9%. It was.
Abstract
Description
Claims
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JP2008517984A JP4997233B2 (ja) | 2006-05-31 | 2007-05-31 | 新規な多核体ポリ(ホルミルフェノール)類の製造方法 |
US12/984,215 USRE43067E1 (en) | 2006-05-31 | 2007-05-31 | Method for producing new polynuclear poly(formylphenol) |
US12/299,902 US7750190B2 (en) | 2006-05-31 | 2007-05-31 | Method for producing new polynuclear poly(formylphenol) |
KR1020087026189A KR101437183B1 (ko) | 2006-05-31 | 2007-05-31 | 신규한 다핵체 폴리(포르밀페놀)류의 제조방법 |
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JPH05339191A (ja) * | 1992-06-11 | 1993-12-21 | Shiratori Seiyaku Kk | アルデヒド類の製造法 |
JPH0761948A (ja) * | 1993-06-14 | 1995-03-07 | Takeda Chem Ind Ltd | α,β−不飽和アルデヒドの製造法 |
JP2002193872A (ja) * | 2000-12-27 | 2002-07-10 | Sumika Fine Chemicals Co Ltd | α,α,α−トリフルオロメチルフェニル置換安息香酸の製造方法 |
JP2003300922A (ja) * | 2002-04-08 | 2003-10-21 | Honshu Chem Ind Co Ltd | トリメチロール化トリフェノール類 |
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US3833660A (en) * | 1972-04-26 | 1974-09-03 | Gen Electric | Process for making aromatic aldehydes |
DE2620254C2 (de) | 1976-05-07 | 1984-03-15 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Hydroxybenzaldehyden |
GB9108221D0 (en) | 1991-04-18 | 1991-06-05 | Ici Plc | Compound preparation and use |
AU2003283214A1 (en) | 2002-11-29 | 2004-06-23 | Aarhus Universitet | (bio) organic oligomers for the preparation of macromolecules |
US7586009B2 (en) * | 2005-02-25 | 2009-09-08 | Honshu Chemical Industry Co., Ltd. | Bis-(hydroxybenzaldehyde) compound and novel polynuclear polyphenol compound derived therefrom and method for production thereof |
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JPH05339191A (ja) * | 1992-06-11 | 1993-12-21 | Shiratori Seiyaku Kk | アルデヒド類の製造法 |
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JP2002193872A (ja) * | 2000-12-27 | 2002-07-10 | Sumika Fine Chemicals Co Ltd | α,α,α−トリフルオロメチルフェニル置換安息香酸の製造方法 |
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US20090182175A1 (en) | 2009-07-16 |
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USRE43067E1 (en) | 2012-01-03 |
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