Classifications

• • 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
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • 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

Definitions

• the present invention relates to a method for producing trisphenols. More specifically, the present invention relates to 1,1,3-characteristics characterized by reacting 2-cycloalkene-1-ones or 3-hydroxycycloalkane-1-ones with phenols in the presence of a catalyst. The present invention relates to a method for producing tris (hydroxyphenyl) cycloalkanes.
• a method for producing a trisphenol having a cycloalkane as a central skeleton for example, a phenol and a ketone having a cycloalkane skeleton substituted with a hydroxyphenyl group are reacted in the presence of an acidic catalyst to form a cycloalkane skeleton. It is known to employ a reaction in which the carbon atom of the carbonyl group that forms is substituted with two hydroxyphenyl groups (Patent Document 1).
• Patent Document 1 does not describe any method for producing a raw material, but among the above-mentioned ketones that are raw materials, cyclic ketones in which a hydroxyphenyl group is bonded to the 3-position of cycloalkanone are: It is a compound that is difficult to produce industrially. For example, as described in Tetrahedron, 55 (1999), 6657, such ketones are obtained by using expensive palladium compounds and phosphorus compounds, and Journal of Organic Chemistry, 56 (1991). In the method of Journal of Chemical Research, Synopses 366 (1995), it is produced from the cyclic unsaturated ketone in one reaction. However, the silver compound necessary for the low yield is also obtained. Neither small amount but any industrially suitable production method has been obtained.
• Non-patent Document 1 an addition product of phenol to an ⁇ , ⁇ -unsaturated bond can be obtained by reacting an alkylphenol with an ⁇ , ⁇ -unsaturated ketone.
• Non-patent Document 1 a method for producing trisphenols from ⁇ , ⁇ -unsaturated aldehyde and phenols is also known, but it is not a method using a ketone (Patent Documents 2 and 3). .
• the present invention provides a process in which 1,1,3-tris (hydroxyphenyl) cycloalkanes can be industrially obtained from ⁇ , ⁇ -unsaturated cyclic ketones or hydroxy-substituted saturated cyclic ketones in a one-step reaction. It is an object to provide a method.
• the raw materials are 2-cycloalkene-1-ones that are ⁇ , ⁇ -unsaturated cyclic ketones or hydroxy-substituted saturated cyclic ketones.
• -1,1,3-tris (hydroxyphenyl) under reaction conditions that can be industrially carried out in one step by using -hydroxycycloalkane-1-ones and reacting them with phenols in the presence of a catalyst
• the present inventors have found that cycloalkanes can be produced and completed the present invention.
• the present invention is as follows. 2-cycloalkene-1-ones represented by the following general formula (1) or 3-hydroxycycloalkane-1-ones represented by the following general formula (2) and the following general formula (3)
• R 1 represents a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• R 2 represents an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• n represents an integer of 1 to 9.
• R 1 , R 2 , m and n are the same as those described above.
• R 3 represents an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom, and when a is 2 or more, R 3 s may be the same or different, and a represents an integer of 0 to 4 B represents an integer of 1 or 2, provided that 1 ⁇ a + b ⁇ 5.
• R 1 , R 2 , R 3 , a, b, m and n are the same as those
• an ⁇ , ⁇ -unsaturated cyclic ring is obtained without using industrially difficult or / and expensive and special raw materials, or without a complicated and long reaction step that is difficult to implement industrially.
• a ketone or a hydroxy group-substituted saturated cyclic ketone as a raw material and reacting this with a phenol, a hydroxyphenyl group is formed at the 1,3-position of the cycloalkane ring by a one-step reaction process from the cyclic ketone.
• Trisphenols can be produced. This eliminates the need for the reaction and purification steps for producing raw material ketones from ⁇ , ⁇ -unsaturated ketones and the like, which have been necessary conventionally. Furthermore, trisphenols can be obtained in high yield by selecting preferable conditions and the like.
• the process for producing 1,1,3-tris (hydroxyphenyl) cycloalkanes represented by the following general formula (4) of the present invention is a 2-cycloalkene-1-one represented by the following general formula (1). Or a 3-hydroxycycloalkane-1-one represented by the following general formula (2) and a phenol represented by the following general formula (3) in the presence of a catalyst.
• R 1 represents a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• R 2 represents an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• n represents an integer of 1 to 9.
• R 1 , R 2 , m and n are the same as those described above.
• R 3 represents an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom, and when a is 2 or more, R 3 s may be the same or different, and a represents an integer of 0 to 4)
• B represents an integer of 1 or 2, provided that 1 ⁇ a + b ⁇ 5.
• R 1 , R 2 , R 3 , a, b, m and n are the same as
• R 1 represents a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• R 2 represents an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• m 0-2 of an integer may be the same or different and each R 2 is the case where the entire ring R 2 is multiply substituted.
• R 1 and R 2 are alkyl groups
• examples of the alkyl group include linear or branched alkyl groups having 1 to 12 carbon atoms, or cycloalkyl groups having 5 to 12 carbon atoms. be able to.
• preferred alkyl groups for R 1 and R 2 are linear or branched alkyl groups having 1 to 8 carbon atoms, or cycloalkyl groups having 5 to 6 carbon atoms, and particularly preferred.
• the alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms.
• a substituent such as a halogen atom, an alkoxyl group, or a phenyl group may be bonded to the carbon atom within a range not impairing the effects of the present invention.
• the alkyl group having a substituent are as follows. Examples include benzyl group, methoxyethyl group, 3-chloropropyl group and the like. Moreover, it is not necessary to substitute.
• R 1 and R 2 are alkoxyl groups
• examples of the alkoxyl group include linear or branched alkoxyl groups having 1 to 12 carbon atoms, or cycloalkoxyl groups having 5 to 12 carbon atoms.
• preferred alkoxyl groups are linear or branched alkoxyl groups having 1 to 4 carbon atoms, or cycloalkoxyl groups having 5 to 6 carbon atoms, and particularly preferred alkoxyl groups include carbon atoms. It is an alkoxyl group of the number 1 or 2.
• Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and a cyclohexyloxy group.
• a substituent such as a halogen atom, an alkoxyl group, and a phenyl group may be bonded to the carbon atom within a range not impairing the effects of the present invention.
• Specific examples of the alkoxyl group having a substituent are as follows. Examples include 2-phenylethoxy group, methoxyethoxy group, 2-chloroethoxy group and the like. Moreover, it is not necessary to substitute.
• R 1 and R 2 are aromatic hydrocarbon groups
• examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 12 carbon atoms. Specific examples include a phenyl group, an indenyl group, and a 1-naphthyl group. Of these, a preferred aromatic hydrocarbon group is a phenyl group. In such an aromatic hydrocarbon group, a substituent such as an alkyl group, an alkoxyl group, a phenyl group, or a halogen atom may be bonded to the aromatic hydrocarbon group as long as the effects of the present invention are not impaired. Specific examples of the hydrocarbon group include a biphenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group. Moreover, it is not necessary to substitute.
• R 1 and R 2 are halogen atoms
• specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R 1 is preferably a hydrogen atom or a lower alkyl group, particularly preferably a hydrogen atom.
• R 2 is preferably an alkyl group, an alkoxyl group, or a phenyl group, and more preferably a lower alkyl group such as a methyl group.
• M which is the number of substitutions for R 2 , is preferably 0 for the carbon atom adjacent to the carbonyl group, and 0 or 1 for the other carbon atoms.
• the carbon atom is preferably not adjacent to the carbonyl group, and R 2 is preferably an alkyl group.
• substitution position of R 2 in the entire ring for example, in the case of a 2-cyclohexen-1-one skeleton, the 4-position or / and the 5-position are preferred.
• N which is the number of carbon atoms constituting the ring, is preferably 2 to 4 in terms of good reaction yield.
• a cyclopentene ring, a cyclohexene ring and a cycloheptene ring are preferable, and particularly preferable n is 3.
• Specific examples of the 2-cycloalkene-1-ones represented by the general formula (1) include 2-cyclopenten-1-one, 2-cyclohexen-1-one, and 2-cycloheptene-one.
• 2-cyclopenten-1-one and 2-cyclohexen-1-one are preferred, and 2-cyclohexen-1-one is particularly preferred.
• Such 2-cycloalkene-1-ones include, for example, a method of isomerizing 2-alkylidenecycloalkanone in the presence of a platinum catalyst (Japanese Patent Publication No. 58-42175, etc.), 2- (1-hydroxylalkyl ) A method of dehydrating isomerization of cycloalkane-1-one in the presence of an acidic catalyst or the like (JP-A-56-147740, etc.), a method of cyclocondensing a dicarbonyl compound (JP-A-10-130192, etc.) ) And the like.
• 3-hydroxycycloalkane-1-ones represented by the general formula (2) include 3-hydroxycyclopentanone, 3-hydroxycyclohexanone, 4-methyl-3-hydroxycyclohexanone. 4,4-dimethyl-3-hydroxycyclohexanone, 5,5-dimethyl-3-hydroxycyclohexanone, 4,5-dimethyl-3-hydroxycyclohexanone, 6-methyl-3-hydroxycyclohexanone, 5-methyl-3-hydroxy Cyclohexanone, 2-methyl-3-hydroxycyclohexanone, 4-methyl-3-hydroxycyclopentanone, 5-methyl-3-hydroxycyclopentanone, 2-methyl-3-hydroxycyclopentanone, 4,4-dimethyl- 3-hydroxycyclopentanone, Examples include 4,5-dimethyl-3-hydroxycyclopentanone.
• Such 3-hydroxycycloalkane-1-ones can be obtained by a known method such as a method of ring hydrogenating a polyhydroxyalkylphenol in the presence of a hydrogenation catalyst or the like (Japanese Patent Laid-Open No. 11-60534). Can be easily obtained.
• the alkyl group when R 3 is an alkyl group, the alkyl group may be, for example, one having 1 to 12 carbon atoms. Examples thereof include a linear or branched alkyl group and a cycloalkyl group having 5 to 12 carbon atoms. Preferred alkyl groups are linear or branched alkyl groups having 1 to 8 carbon atoms, or cycloalkyl groups having 5 to 8 carbon atoms, and more preferred alkyl groups are those having 1 to 4 carbon atoms.
• a linear or branched alkyl group, a cycloalkyl group having 5 to 6 carbon atoms, and particularly preferable alkyl groups include primary or secondary alkyl groups having 1 to 4 carbon atoms, and 5 to 6 carbon atoms.
• 6 cycloalkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
• a substituent such as an alkoxyl group, a phenyl group, or a halogen atom may be bonded to the carbon atom within a range that does not impair the effects of the present invention.
• Specific examples of the alkyl group having a substituent Examples include methoxyethyl group, benzyl group, 3-chloropropyl group and the like. Moreover, it is not necessary to substitute.
• R 3 is an alkoxyl group
• examples of the alkoxyl group include a linear or branched alkoxyl group having 1 to 12 carbon atoms or a cycloalkoxyl group having 5 to 12 carbon atoms.
• a preferred alkoxyl group is a linear or branched alkoxyl group having 1 to 8 carbon atoms or a cycloalkoxyl group having 5 to 6 carbon atoms, and particularly preferred alkoxyl groups are those having 1 to 4 carbon atoms.
• a linear or branched alkoxyl group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group and the like.
• a substituent such as an alkoxyl group, a phenyl group, or a halogen atom may be bonded to the carbon atom of the alkoxyl group within a range not impairing the effects of the present invention.
• Specific examples of the alkoxyl group having a substituent Examples thereof include methoxyethoxy group, 2-phenylethoxy group, 2-chloroethoxy group and the like. Moreover, it is not necessary to substitute.
• R 3 is an aromatic hydrocarbon group
• examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 12 carbon atoms. Specific examples include a phenyl group, an indenyl group, a 1-naphthyl group, and a phenyloxy group. Of these, a preferred aromatic hydrocarbon group is a phenyl group. In such an aromatic hydrocarbon group, a substituent such as an alkyl group, an alkoxyl group, a phenyl group, or a halogen atom may be bonded to the aromatic hydrocarbon group as long as the effects of the present invention are not impaired. Specific examples of the hydrocarbon group include 4-methylphenyl group, p-methoxyphenyl group, 4-chlorophenyl group and the like. Moreover, it is not necessary to substitute.
• R 3 is a halogen atom
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• b represents an integer of 1 or 2, and b is preferably 1.
• a represents 0 or an integer of 1 to 4, preferably 0, 1 or 2.
• the position of the substituent is preferably a phenol having no substituent at the para position of the hydroxyl group. When b is 1, there is no substituent at the para position of the hydroxyl group, and at least one of the meta positions of the hydroxyl group has a substituent. More preferred are phenols.
• a preferred phenol is represented by the following general formula (5).
• R 4 represents a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• R 5 represents a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic hydrocarbon group, a halogen atom or a hydroxyl group.
• R 4 and R 5 are an alkyl group, an alkoxyl group, an aromatic hydrocarbon group or a halogen atom
• specific examples of an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a halogen atom Preferred examples and preferred ranges are the same as R 3 .
• R 4 and R 5 are preferably not tertiary alkyl groups, and when one is a tertiary alkyl group, the other is more preferably a hydrogen atom, a primary alkyl group or a secondary alkyl group.
• R 4 and R 5 are an aromatic hydrocarbon group such as a phenyl group.
• the phenols represented by the general formula (3) include phenol, catechol, o-cresol, 2,5-xylenol, 2,6-xylenol, and 2,3,6-trimethyl.
• R 1 , R 2 , R 3 , a, b, m and n are the above The same as those in the general formulas (1) to (3).
• the substitution positions of R 3 , a, b and R 3 of the three hydroxyphenyl groups or / and the substitution positions of the hydroxyl groups may be the same or different, but are preferably the same.
• a preferable trisphenol compound is represented by the following general formula (6). (In the formula, R 1 , R 2 , m and n are the same as those in the general formula (1) or (2), and R 4 and R 5 are the same as those in the general formula (5).)
• the trisphenols represented by the above general formula (4) or the above general formula (6) which are objects of the production method of the present invention, specifically, for example, 1,1,3-tris (4-hydroxyphenyl) cyclopentane 1,1,3-tris (4-hydroxyphenyl) cyclohexane 1,1,3-tris (3-methyl-4-hydroxyphenyl) cyclohexane 1,1,3-tris (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 1,1,3-tris (3,4-dihydroxyphenyl) cyclohexane 1,1,3-tris (3-methyl-4-hydroxyphenyl) cyclopentane 1,1,3-tris (3,5-dimethyl-4 -Hydroxyphenyl) cyclopentane 1,1,3-tris (3-phenyl-4-hydroxyphenyl) cyclopentane 1,1,3-tris (3,4-dihydroxyphenyl) cyclopentane 1,1,3-
• the 2-cycloalkene-1-one represented by the general formula (1) or the 3-hydroxycycloalkane-1- represented by the general formula (2) is used.
• the trisphenol represented by the general formula (4) can be obtained in a one-step reaction process by reacting the ONs with the phenol represented by the general formula (3) in the presence of a catalyst.
• the reaction of obtaining 1,1,3-tris (4-hydroxyphenyl) cyclohexane by the reaction of phenol with 2-cyclohexen-1-one or 3-hydroxycyclohexane-1-one is represented by the following reaction formula (1). Indicated. When two or more types of phenols of the general formula (3) are reacted simultaneously or sequentially, three hydroxyphenyl group substituents, substitution positions and / or the same number of trisphenols and the same trisphenol are mixed. And generate.
• the phenols represented by the general formula (3) and the 2-cycloalkene-1-ones represented by the general formula (1) or the 3-hydroxy represented by the general formula (2) are preferably used in a range of 3 to 50 mol times, more preferably 2-cycloalkene-1-ones or 3-hydroxycycloalkane-1-ones. Is used in the range of 5 to 30 mol times, particularly preferably 8 to 20 mol times, but is not limited thereto.
• the catalyst is preferably an acidic catalyst. However, the present invention is not limited to this.
• the acidic catalyst examples include gaseous, liquid and solid acidic catalysts such as a proton acid catalyst and a Lewis acid catalyst.
• gaseous, liquid and solid acidic catalysts such as a proton acid catalyst and a Lewis acid catalyst.
• a proton acid catalyst examples include hydrogen chloride gas, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and sulfuric anhydride, organic acids such as P-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid or trichloroacetic acid, aluminum chloride, chloride
• metal halides such as iron, heteropolyacids such as phosphotungstic acid and silicotungstic acid, and solid acids such as cation exchange resins.
• hydrochloric acid or hydrogen chloride gas is particularly preferred.
• the amount of acidic catalyst used is not particularly limited.
• the preferred amount used varies depending on the catalyst, and cannot be generally specified.
• the amount is preferably 0.1% relative to 2-cycloalkene-1-ones or 3-hydroxycycloalkane-1-ones. It is used in a range of ⁇ 3 mole times, more preferably 0.2 to 1.0 mole times, particularly preferably 0.3 to 0.6 mole times. In that case, a relatively high concentration of hydrochloric acid such as 35% is preferred.
• a promoter can be used to accelerate the reaction.
• the reaction proceeds without using a cocatalyst, it is preferable to use a cocatalyst from the viewpoint of reaction yield and reaction rate.
• the cocatalyst is preferably a compound having a mercapto group or a polymer compound.
• alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, ⁇ -mercaptopropion, etc.
• Examples thereof include mercaptan carboxylic acids such as acids, cation exchange resins having mercapto groups, and organic polymer siloxanes.
• methyl mercaptan When methyl mercaptan is used, it may be used as an aqueous sodium salt solution.
• the amount of the cocatalyst used is not particularly limited and cannot be generally stated because the appropriate amount varies depending on the reaction conditions and types.
• the amount used is 2-cycloalkene-1-one.
• it is preferably in the range of 0.5 to 50 mol%, more preferably 2 to 30 mol%, particularly preferably 4 to 20 mol% with respect to 3-hydroxycycloalkane-1-ones.
• the reaction temperature is preferably in the range of 0 to 80 ° C., more preferably 10 to 60 ° C., particularly preferably 15 to 50 ° C. Under such reaction conditions, the reaction is carried out with all the raw materials in the reaction system. After the addition, it is preferably completed within about 80 hours.
• a reaction solvent may or may not be used, but it is preferably used when the raw materials and the catalyst are not sufficiently mixed because the melting point of phenols is high.
• the type and addition amount of the solvent are not particularly limited as long as the effects of the present application are not impaired. Specific examples of preferable reaction solvents include water, methanol, ethanol, and 1-propanol.
• reaction solvent is preferably used in a range of 0.1 to 20 moles per 2-cycloalkene-1-one or 3-hydroxycycloalkane-1-one.
• the raw material charging method and the reaction method are not particularly limited, but the reaction can be carried out according to the method used in the reaction of ordinary bisphenols and trisphenols.
• the raw material, the catalyst, and if necessary, the cocatalyst and the reaction solvent may be charged all at once into the reaction vessel, and then heated to the reaction temperature in an inert gas atmosphere, and the reaction may be performed with stirring.
• the raw material ketone 2-cycloalkene-1-one or 3-hydroxycycloalkane in an inert gas atmosphere is charged into a reaction vessel charged with the raw material phenols, an acidic catalyst and, if necessary, a cocatalyst and a reaction solvent.
• a mixture of -1-ones or their raw material ketone and phenols or a solvent may be added successively at the reaction temperature. The latter method is preferable from the viewpoint of reaction yield.
• a predetermined amount of phenols, an acidic catalyst and, if necessary, a cocatalyst and a reaction solvent are charged into a reaction vessel, and the temperature is raised to a predetermined reaction temperature while stirring under a nitrogen stream,
• 2-cycloalkene-1-ones or 3-hydroxycycloalkane-1-ones are added successively.
• an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous ammonia solution is added to the reaction end solution to neutralize the acidic catalyst.
• a solvent such as an aromatic hydrocarbon or aliphatic ketone that separates from water is added, and the oil layer obtained by separating and removing the aqueous layer is cooled, crystallized or precipitated, and then filtered.
• the oil layer obtained by separating and removing the aqueous layer is obtained by repeating the operation of separating and removing the aqueous layer once or a plurality of times after adding water, stirring and washing again, if necessary.
• the obtained oil layer is cooled, crystallized or precipitated, and filtered to obtain the target crude crystal or solid.
• the oil layer obtained by separating and removing the aqueous layer was distilled to distill off the solvent and unreacted phenols, and then the residue was dissolved in an appropriate solvent, and the resulting solution was cooled. After crystallizing or precipitating, it may be filtered, and when it is difficult to crystallize the target product, the residue obtained by distillation can be cooled to obtain a crude product.
• an appropriate solvent may be added to the solution after neutralization with the aqueous alkali solution to cause crystallization or precipitation.
• a known purification method can be used to obtain high-purity trisphenols from the crude crystal, solid or crude product.
• the trisphenol obtained by the above method is dissolved in an aromatic hydrocarbon solvent such as toluene, an alcohol solvent such as methanol, an aliphatic ketone solvent such as acetone or methyl isobutyl ketone, and cooled and recrystallized as it is. Or after adding a poor solvent, this can be cooled and recrystallized, and the precipitated crystal can be separated by filtration to obtain a high-purity product of trisphenols.
• the target trisphenol it may be obtained as an adduct crystal (adduct crystal) with the solvent used or the raw material phenols.
• the produced trisphenols may have asymmetric carbon atoms depending on the structure of the raw material ketone.
• the trisphenols are usually obtained as a racemic mixture.
• the obtained racemic mixture trisphenol can be separated using a known method such as optically active column separation to obtain an enantiomer or diastereomer of the trisphenol.
• Example 1 [Synthesis of 1,1,3-tris (4-hydroxyphenyl) cyclopentane] A test tube was charged with 22 g of phenol, 1.3 g of 35% hydrochloric acid and 0.1 g of dodecyl mercaptan, and the temperature was raised to 40 ° C. in a nitrogen atmosphere. Then, 2 g of 2-cyclopenten-1-one was added. Stir at 50 ° C. for 50 hours. As a result of analyzing the reaction completion liquid by high performance liquid chromatography, the compositional value of the target product (area percentage / excluding phenol) was 15%. The yield calculated from this composition value is 20 mol% (vs. 2-cyclopenten-1-one).
• Example 2 to Example 6 were obtained in the same manner.
• Example 2 [Synthesis of 1,1,3-tris (4-hydroxyphenyl) cyclohexane]
• a test tube was charged with 20 g of phenol, 2 g of 35% hydrochloric acid and 0.1 g of dodecyl mercaptan, and the temperature was raised to 40 ° C. in a nitrogen atmosphere. Then, 2 g of 2-cyclohexen-1-one was added. The reaction was stirred for 30 hours.
• the composition value of 1,1,3-tris (4-hydroxyphenyl) cyclohexane area percentage / excluding phenol was 68%. The yield calculated from this composition value is 77% (vs. 2-cyclohexen-1-one).
• Example 3 [Synthesis of 1,1,3-tris (4-hydroxyphenyl) cyclohexane] 1412 g of phenol, 78.2 g of 35% hydrochloric acid, 15.2 g of dodecyl mercaptan, and 144 g of methanol were charged into a 3 liter four-necked flask, and the liquid temperature was kept at 30 to 35 ° C. in a nitrogen atmosphere while 2-cyclohexene-1- 144 g of ON was added dropwise over 10 hours, and after completion of the addition, the mixture was stirred at 30 ° C. for 46 hours.
• Example 4 [Synthesis of 1,1,3-tris (4-hydroxyphenyl) cyclohexane] 41.6 g of phenol, 3.2 g of 35% hydrochloric acid and 0.5 g of dodecyl mercaptan were charged into a 200 ml four-necked flask, heated to 40 ° C. under a nitrogen atmosphere, and then 10.7 g of 3-hydroxycyclohexane-1-one was added. The solution was added dropwise over 3 hours, and after completion of the addition, the mixture was reacted by stirring at 40 ° C. for 79 hours.
• Example 5 [Synthesis of 1,1,3-tris (3-methyl-4-hydroxyphenyl) cyclohexane] Orthocresol 1513.4 g, 35% hydrochloric acid 73 g, dodecyl mercaptan 14.2 g, and methanol 134.4 g were charged into a 3 liter four-necked flask, and the liquid temperature was kept at 30 to 32 ° C. under a nitrogen atmosphere. 134.5 g of cyclohexen-1-one was added dropwise over 3.5 hours. After completion of dropping, the mixture was stirred at 30 to 32 ° C. for 22 hours.
• the precipitated adduct crystals are filtered off at room temperature, dried, and the target 1,1,3-tris (3-methyl-4- 522.5 g of hydroxyphenyl) cyclohexane were obtained as white adduct crystals.
• the amount of solvent in the adduct crystal was 16% by weight.
• 1,1,3-tris (3 The purity of -methyl-4-hydroxyphenyl) cyclohexane was 99.2% (excluding solvent).
• Example 6 [Synthesis of 1,1,3-tris (3-phenyl-4-hydroxyphenyl) cyclohexane] Charge 177 g of 2-phenylphenol, 0.5 g of dodecyl mercaptan, and 17.7 g of methanol into a 1-liter four-necked flask and raise the liquid temperature to 42 ° C. in a nitrogen atmosphere. Blowed until saturated. While maintaining the internal temperature at 39 to 41 ° C., 10.1 g of 2-cyclohexen-1-one was added dropwise thereto over 2 hours, and after completion of the addition, the mixture was stirred at 39 to 41 ° C. for 25 hours while blowing hydrogen chloride gas. .
• Comparative Example 1 [Reaction of phenol with 4-hexen-3-one] After adding 19 g of phenol, 1.0 g of 35% hydrochloric acid and 0.1 g of dodecyl mercaptan to a test tube and raising the temperature to 35 ° C., 2 g of 4-hexen-3-one was added. Stir for hours. The reaction solution was analyzed in the same manner as in Example 1, but formation of trisphenol could not be confirmed.

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