CN109195936A - The manufacturing method of alcohols with fluorene skeleton - Google Patents
The manufacturing method of alcohols with fluorene skeleton Download PDFInfo
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- CN109195936A CN109195936A CN201780033105.9A CN201780033105A CN109195936A CN 109195936 A CN109195936 A CN 109195936A CN 201780033105 A CN201780033105 A CN 201780033105A CN 109195936 A CN109195936 A CN 109195936A
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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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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Abstract
The present invention provides a kind of manufacturing method of alcohols indicated with general formula (2), the manufacturing method reacts the phenol indicated with general formula (1) with alkylene carbonate esters in the presence of being selected from least one of the ketone of diol bisether and carbon atom number 4~12 compound.In general formula (1) and (2), R1And R2It is identical or different respectively, indicate halogen atom, alkyl or alkoxy.n1And n2It is identical or different respectively, indicate 0 or 1~3 integer.In general formula (2), R3And R4It is identical or different respectively, indicate the alkylidene optionally with branch of carbon atom number 2~4.
Description
Technical field
The present invention relates to be suitable for being formed the monomer of resin (optical resin) and processability, productivity are excellent has
The manufacturing method of the alcohols of fluorene skeleton, wherein above-mentioned resin is the resin for constituting the optical components such as optical lens, optical film.
Background technique
Using the alcohols with fluorene skeleton as the polycarbonate of starting monomer, polyester, polyacrylate, polyurethane, epoxy
The resin materials such as resin are since optical characteristics, heat resistance etc. are excellent, light new as optical lens, optical sheet etc. in recent years
Material is learned to attract attention.Wherein, as substituent group there are double aryl fluorenol classes of phenyl to manufacture by what is indicated using the following general formula (2)
Resin due in the optical characteristics such as refractive index, heat resistance, water resistance, chemical-resistant, electrical characteristics, mechanical property, dissolubility
Etc. it is excellent in terms of various characteristics, therefore attract attention (such as Japanese Unexamined Patent Publication 07-149881 bulletin (patent document 1), day
This special open 2001-122828 bulletin (patent document 2)).
[changing 1]
(in formula, R1And R2It is identical or different respectively, indicate halogen atom, alkyl or alkoxy.n1And n2Respectively it is identical or
Difference indicates 0 or 1~3 integer.R3And R4It is identical or different respectively, indicate the Asia optionally with branch of carbon atom number 2~4
Alkyl.)
On the other hand, the manufacturing method as the alcohols indicated with above-mentioned general formula (2), in patent document 2, record make with
The method that the oxybenzene compound that the following general formula (1) indicates is reacted with alkylene oxides:
[changing 2]
(in formula, R1、R2、n1、n2Meaning it is as described above.)
However, the alcohols indicated with above-mentioned general formula (2) obtained using this method the secondary ring for generating 3 molecules or more in large quantities
Oxygen alkane participates in the compound (being sometimes referred to as polymer below) of reaction, as a result, its purity is low, it is difficult to be obtained with high-purity
The alcohols indicated with above-mentioned general formula (2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 07-149881 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2001-122828 bulletin
Summary of the invention
Problem to be solved by the invention
The object of the present invention is to provide a kind of as substituent group with phenyl, high-purity double aryl fluorenol classes
Industrialization production method.
The method for solving problem
Further investigation has been repeated in order to solve the problem above-mentioned in the inventors of the present invention, as a result, it has been found that, by being selected from two
In the presence of at least one of alcohol diether and the ketone of carbon atom number 4~12 compound, make the benzene indicated with above-mentioned general formula (1)
Phenols is reacted with alkylene carbonate esters, can solve the above problem.It specifically include invention below.
[1] a kind of manufacturing method is the manufacturing method of the alcohols indicated with the following general formula (2),
[changing 4]
(in formula, R1、R2、n1、n2Meaning it is as described below.R3And R4It is identical or different respectively, indicate carbon atom number 2~4
Optionally with the alkylidene of branch.)
In the presence of being selected from least one of the ketone of diol bisether and carbon atom number 4~12 compound, make following
The phenol for stating general formula (1) expression is reacted with alkylene carbonate esters:
[changing 3]
(in formula, R1And R2It is identical or different respectively, indicate halogen atom, alkyl or alkoxy.n1And n2Respectively it is identical or
Difference indicates 0 or 1~3 integer.)
[2] according to the manufacturing method recorded in [1], wherein reaction temperature is 110~135 DEG C.
It [3] after the reaction further include that water is added into reaction product according to the manufacturing method recorded in [1] or [2]
And strong alkaline substance and mixed process.
Invention effect
In accordance with the invention it is possible to which manufacturing has phenyl, high-purity double aryl fluorenol classes as substituent group.Especially root
According to the present invention, carbonic acid remove using crystallization as the industrial method of representative, more than 3 molecules Asia is difficult to be utilized due to being able to suppress
The generation of compound (polymer) obtained by alkyl esters are reacted with the phenol indicated with above-mentioned general formula (1), therefore can be with
The alcohols of industrially scalable manufacture high-purity indicated with above-mentioned general formula (2).In addition, manufacturing method according to the invention, due to
Compared with known method, reaction speed is increased substantially, therefore economically can advantageously be manufactured with above-mentioned
The alcohols that general formula (2) indicates.Simultaneously as the alcohols indicated with above-mentioned general formula (2) obtained using the manufacturing method of the present invention
It has both and colours few feature, be thus particularly suited for setting as polycarbonate, polyester, polyacrylate, polyurethane, epoxy resin etc.
The raw material of rouge material uses.
Specific embodiment
As the halogen atom of the phenol indicated with above-mentioned general formula (1), fluorine, chlorine, bromine, iodine etc. may be exemplified out.As
Alkyl may be exemplified out methyl, ethyl, propyl, butyl etc. with the alkyl of linear chain or branched chain, cyclopenta, cyclohexyl, suberyl,
Cyclic alkyls such as cyclooctyl etc. in these alkyl, are examined in terms of the availability of the phenol indicated with above-mentioned general formula (1)
Consider, preferably the alkyl with linear chain or branched chain of carbon atom number 1~6.As alkoxy may be exemplified out methoxyl group, ethyoxyl,
The alkoxy of the carbon atom numbers such as butoxy 1~6.Indicate the n for replacing radix1And n2It is identical or different respectively, indicate 0 or 1~3
Integer is preferably 0 or 1 from the aspect of the availability of the phenol indicated with above-mentioned general formula (1).In n1And/or n2It is 2 or 3
In the case where, corresponding substituent group (R1And/or R2) can be the same or different respectively.
In the above-mentioned phenol indicated with above-mentioned general formula (1), from the aspect of the availability of the phenol, preferably
For following phenol, that is, do not have substituent group (n1=n2=0) or in respective aromatic proton respectively there is a substituent group
(n1=n2=1) and the substituent group be carbon atom number 1~6 the alkyl with linear chain or branched chain phenol.
Commercially available product can be used with the phenol that above-mentioned general formula (1) indicates, alternatively, it is also possible in the presence of acid catalyst
Under, so that Fluorenone is reacted and is manufactured with corresponding phenol.
Diol bisether used in the present invention has the structure indicated with following formula (3):
R5- O (CH2R7O)n- R6 (3)
(in formula, R5And R6It is identical or different respectively, indicate the alkyl of the optionally carbon atom number 1~4 with branch, R7It indicates
The optionally alkylidene of the carbon atom number 1~3 with branch.N indicates 1~4 integer.)
As such diol bisether, may be exemplified out glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether,
Dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether, diethylene glycol
Fourth methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ethylene glycol ether, triethylene glycol fourth methyl ether, tetraethylene glycol two
Methyl ether etc..
The ketone of so-called carbon atom number 4~12 used in the present invention, specifically, may be exemplified out methyl ethyl ketone, first
The chains such as base isobutyl ketone, methyl isoamyl ketone, 2-HEPTANONE, methyln-hexyl ketone, diisobutyl ketone ketone, cyclopentanone, cyclohexanone, ring
The ring-type ketone such as heptanone, cyclooctanone, cyclononanone, ring decanone, cyclododecanone.It should be noted that in use carbon atom number less than 4
Ketone in the case where, reaction is without or even if carrying out, reaction speed also becomes very slow, in addition, using carbon atom
In the case where the ketone of 13 or more number, the generation of polymer can not be inhibited.
In at least one of the above-mentioned ketone of diol bisether and carbon atom number 4~12 compound, due to can
Inexpensively to obtain, thus preferably glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, dimethyl ether,
Diethylene glycol ethylmethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether, diethylene glycol fourth methyl ether, tripropylene glycol two
Methyl ether, triethylene glycol dimethyl ether, dibutyl ethylene glycol ether, triethylene glycol fourth methyl ether, tetraethyleneglycol dimethyl ether methyl ethyl ketone, methyl are different
Butyl ketone, methyl isoamyl ketone, 2-HEPTANONE, methyln-hexyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone.In addition, the compound
Usage amount is usually 0.05~3 times of weight, preferably 0.08~1 relative to 1 times of weight of phenol indicated with above-mentioned general formula (1)
Times of weight.More than 0.05 times of weight, the generation inhibitory effect of polymer can be fully played.On the other hand, exist
In the case that usage amount is greater than 3 times of weight, although high-purity and the few alcohol indicated with above-mentioned general formula (2) of coloring can be manufactured
Class, however the effect to match with additive amount can not be embodied, therefore in order to economically advantageously obtain with above-mentioned general formula (2) table
Usage amount is preferably set as 3 times of weight or less by the alcohols shown.
So-called alkylene carbonate esters of the invention indicate the alkylene carbonate class of carbon atom number 3~5, specifically example
It such as may be exemplified out ethylene carbonate, propylene carbonate, butylene carbonate.In these alkylene carbonate esters from availability, from
The wellness of setting property considers, can suitably use ethylene carbonate.In addition, alkylene carbonate esters phase used in the present invention
For 1 mole of the phenol that is indicated with above-mentioned general formula (1) usually using 2~10 moles, it is preferable to use 2~4 moles.By using
2 moles or more, sufficient reaction speed can be obtained, by by usage amount be set as 10 moles hereinafter, can economically more added with
The alcohols indicated with above-mentioned general formula (2) is obtained sharply.
When reacting the phenol indicated with above-mentioned general formula (1) with alkylene carbonate esters, as needed in alkalization
It is reacted in the presence of conjunction object.As alkali compounds used in this reaction, carbonate, bicarbonate may be exemplified out
More specifically class, metal hydroxides class, organic bases etc. can enumerate potassium carbonate, sodium carbonate, carbonic acid as carbonate
Lithium, cesium carbonate etc. may be exemplified out saleratus, sodium bicarbonate, lithium bicarbonate, caesium bicarbonate etc. as bicarbonate salts, make
It may be exemplified out sodium hydroxide, potassium hydroxide, lithium hydroxide etc. for metal hydroxides class, may be exemplified out as organic bases
Triethylamine, dimethyl aminopyridine, triphenylphosphine, 4 bromide, tetramethyl ammonium chloride etc..In these alkali compounds from
From the aspect of the wellness of disposition property, potassium carbonate, sodium carbonate, triphenylphosphine can be suitably used.Use these alkalizations
Usage amount when conjunction object is relative to 1 mole of the phenol indicated with above-mentioned general formula (1) usually 0.01~1.0 mole, preferably
0.03~0.2 times mole.
It, as needed, can also be at least one in the ketone selected from diol bisether and carbon atom number 4~12 in the present invention
Kind compound together, and uses inert organic solvents.As the inert organic solvents, aromatic hydrocarbon, halogenated virtue may be exemplified out
Fragrant race's hydro carbons, aliphatic hydrocarbon, halogenated aliphatic hydro carbons, ethers (wherein not including diol bisether class), esters, aliphatic nitrile
Class, amides, sulfoxide type etc..More specifically, toluene, dimethylbenzene, mesitylene etc. be may be exemplified out as aromatic hydrocarbon,
It may be exemplified out chlorobenzene, dichloro-benzenes etc. as halogenated aromatic hydrocarbon, may be exemplified out pentane, hexane, heptane as aliphatic hydrocarbon
Deng may be exemplified out methylene chloride, 1,2- dichloroethanes etc. as halogenated aliphatic hydro carbons, may be exemplified out two as ethers
Ether, diisopropyl ether, methyl tertiary butyl ether, cyclopentyl methyl ether, diphenyl ether etc. may be exemplified out ethyl acetate, acetic acid as esters
Butyl ester etc. may be exemplified out acetonitrile etc. as aliphatic nitrile, as amides may be exemplified out n,N-Dimethylformamide,
N,N-dimethylacetamide etc. may be exemplified out dimethyl sulfoxide etc. as sulfoxide type.From acquisition in these inert organic solvents
Property, disposition property wellness consider, can suitably using the boiling point under 101.3kPa be 110 DEG C or more aromatic hydrocarbon or
Ethers.One kind can be used in these organic solvents, or can according to need be used in mixed way it is two or more.Have for and with these
Usage amount when solvent is usually 0.1~5 weight relative to 1 times of weight of oxybenzene compound indicated with above-mentioned general formula (1)
Times, preferably 0.5~3 times of weight.
The phenol indicated with above-mentioned general formula (1) and alkylene carbonate esters react usually 30~150 DEG C, preferably exist
110~135 DEG C of implementations.
Comprising utilizing the reaction solution of the alcohols obtained by the above method indicated with above-mentioned general formula (2) can be directly as resin
Raw material (monomer), medical pesticide material (intermediate) etc. use, and can also implement the post-processing such as washing, adsorption treatment or analysis
After brilliant, column chromatography purification etc., it will be taken out using the alcohols that above-mentioned general formula (2) indicate as crystal.In addition, due to implementing after the reaction
Water and strong alkaline substance are added into the reaction solution of the alcohols comprising indicating with above-mentioned general formula (2) and mixed process (has below
When also referred to as alkali cleaning process), and the by-product destruction that will be generated in reaction is thus resulting with above-mentioned logical to further increase
The purity for the alcohols that formula (2) indicates, therefore alkali cleaning process is preferably implemented.Hereinafter, being described in detail to alkali cleaning process.
So-called strong alkaline substance used in alkali cleaning process of the invention refers to the alkali of dissociation constant of a base (pKb) less than 1
Compound.As these strong alkaline substances, for example, the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change alkaline-earth metals hydroxide such as calcium, barium hydroxide etc., particularly preferred sodium hydroxide, potassium hydroxide.These strong alkaline substances
One kind can be used, or can according to need be used in mixed way it is two or more.
As the usage amount of strong alkaline substance used in alkali cleaning process, for example, relative to used in reaction with above-mentioned
1 mole of phenol of general formula (1) expression, usually 0.3~4 mole, preferably 0.4~2.5 mole.By by strong alkaline substance
Usage amount be set as 0.3 mole or more, the decomposition of by-product can be promoted, additionally by being set as 4 moles hereinafter, alkali can be mitigated
The burden of wastewater treatment after cleaning process.
The usage amount of the water used in alkali cleaning process, such as the water and strong alkaline substance by investment reaction solution
Concentration generate, strong alkaline substance in water phase, usually 1~50 weight %, preferably 3~30 weight %.As water phase
In strong alkaline substance concentration, by being set as 1 weight % or more, thus by-product discomposing effect improve, by being set as 50
Weight % is hereinafter, it is possible thereby to inhibit the decomposition of the alcohols with fluorene skeleton indicated with above-mentioned general formula (2), furthermore it is possible to subtract
The burden of light wastewater treatment, therefore preferably.It should be noted that strong alkaline substance used in alkali cleaning process and water can lead to
It crosses and water and strong alkaline substance is put into reaction solution respectively and the aqueous solution of given concentration is mixed and be made after investment, it can also be with
Use the aqueous solution for being pre-mixed water and strong alkaline substance.
When implementing alkali cleaning process, as needed, phase transfer catalyst also can be used.Turn as the phase being able to use
Shifting catalyst may be exemplified out quaternary ammonium salt, quaternary alkylphosphonium salt, pyridiniujm, crown ether etc..It should be noted that implementing alkali scavenger
When sequence, there is at least one of ketone selected from diol bisether and carbon atom number 4~12 used in reaction process to change in remaining
In the case where closing object, even if not using phase transfer catalyst, the by-product that can also generate in decomposition reaction.
When implementing alkali cleaning process, the organic solvent that can be separated from water can be used together as needed.As can be with
The organic solvent of water separation, for example, benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon, chlorobenzene, dichloro-benzenes
Aliphatic hydrocarbons, methylene chloride, chloroform, 1, the 2- dichloroethanes etc. such as equal halogenated aromatics hydro carbons, pentane, hexane, heptane are halogenated
The ethers such as hydro carbons, diethyl ether, diisopropyl ether, methyl tertiary butyl ether, cyclopentyl methyl ether, diphenyl ether, ethyl acetate, n-butyl acetate etc.
Aliphatic ketone such as the alcohols such as esters, butanol, amylalcohol, hexanol, enanthol, methyl iso-butyl ketone (MIBK) etc..It is wherein preferably aromatic hydrocarbon
Class, halogenated aromatic hydro carbons, ketone, ethers, particularly preferably toluene, dimethylbenzene.One kind can be used in these organic solvents, or
Person can according to need be used in mixed way it is two or more.For the organic solvent that these can be separated from water, in reaction work above-mentioned
At least one of ketone used in sequence selected from diol bisether and carbon atom number 4~12 compound and as needed simultaneously
In the case that inert organic solvents can be separated from water, can using the solvent as used in alkali cleaning process, can
The organic solvent being separated from water.
As the usage amount for the organic solvent that can be separated from water, relative to contained in reaction solution with above-mentioned general formula (2)
1 times of weight of alcohols of expression is 40 times of weight or less.By the way that the usage amount of organic solvent is set as 40 times of weight hereinafter, can promote
Into the decomposition of impurity, in addition economy is improved, therefore preferably.And with can be separated from water organic solvent in the case where, can
To carry out the addition of water, strong alkaline substance and the organic solvent that can be separated from water simultaneously, can also add later it is any one
It is a.In the case where the organic solvent that addition can be separated from water, if added after the organic solvent that addition can be separated from water
Reinforce alkaline matter, then crystal is difficult to be precipitated, therefore the implementation of alkali cleaning process becomes to be more easier.
Alkali cleaning process is usually at 0~150 DEG C, preferably in 60~120 DEG C of implementations.By will implement temperature be set as 0 DEG C with
On, the decomposition of by-product can be promoted, by being set as 150 DEG C hereinafter, being able to suppress the resulting alcohol indicated with above-mentioned general formula (2)
The coloring of class, therefore preferably.
After implementing alkali cleaning process, when implementing alkali cleaning process not using the feelings for the organic solvent that can be separated from water
Under condition, the organic solvent that can be separated from water, further progress mixing are added.
After alkali cleaning process, will the organic phase comprising the alcohols indicated with above-mentioned general formula (2) it is separated from the water, removing
Water phase.
It, can be direct by the organic phase of the resulting alcohols comprising being indicated with above-mentioned general formula (2) after alkali cleaning process
The alcohols indicated with above-mentioned general formula (2) is taken out after concentration, also can use the post-processing such as washing, adsorption treatment or crystallization, column color
The conventional methods such as spectrum purification are purified.
The HPLC of the alcohols indicated obtained in method of the invention with above-mentioned general formula (2) determined using aftermentioned method
Purity is usually 90% or more, and preferably 95% or more, more preferably 98% or more.In addition, utilizing the measurement of aftermentioned method
YI value is usually 10 hereinafter, preferably 7 hereinafter, therefore can be used as polycarbonate, polyester, polyacrylate, polyurethane, epoxy
The raw material of the resin materials such as resin suitably uses.
Embodiment
Examples and Comparative Examples will be enumerated below and the present invention will be specifically described, however the present invention not by they
Any restriction.It should be noted that implementing various measurements using following methods in example.In addition, following embodiment, comparative example,
The production rate (survival rate) and purity of each ingredient recorded in reference example are the areas hundred of the HPLC determined under the following conditions
Point rate value (the correction area fraction values for eliminating the peak of the solvent in reaction solution).
(1) HPLC purity
Device: Shimadzu Seisakusho Ltd. LC-2010A,
Chromatographic column: SUMIPAX ODS A-211 (5 μm, 4.6mm φ × 250mm),
Mobile phase: pure water/acetonitrile (acetonitrile 30% → 100%),
Flow: 1.0ml/min, column temperature: 40 DEG C, Detection wavelength: UV 254nm.
(2) YI value
The crystal 12g of the alcohols indicated with above-mentioned general formula (2) is dissolved in the N of 99 weight % of purity or more, N- dimethyl
In formamide 30ml, the YI value (yellow chromaticity) of resulting n,N-Dimethylformamide solution is determined under the following conditions.
Device: colour difference meter (Japanese electricity Se industrial group system, SE6000),
The colorimetric pool used: optical path length 33mm quartz cuvette pond.
It should be noted that in order not to make the coloring of n,N-Dimethylformamide itself used in measurement to measured value
It impacts, measures the tone of n,N-Dimethylformamide in advance and be corrected (blank determination).
After implementing above-mentioned blank determination, sample is measured, by resulting value as YI value of the invention.
1 > of < embodiment
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 13.1g
(0.149mol), toluene 45g and triethylene glycol dimethyl ether 15g, are warming up to 115 DEG C, after mutually synthermal stirring 5 hours, benefit
Reaction solution is analyzed with HPLC.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 93%；
Polymer: 0.7%.
The sodium hydrate aqueous solution 30g of toluene 30g, 12 weight % are added into resulting reaction solution, it is small in 85 DEG C of stirrings 1
When after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, resulting result is expressed as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 97%；
Polymer: 0.7%.
Water 30g is added into resulting organic phase, is stirred 30 minutes at 80~85 DEG C, after standing, separates water-yielding stratum.Repeatedly
After carrying out 3 identical operations, resulting organic layer is concentrated, thus removes solvent, obtains concentrate.Into resulting concentrate
Addition toluene 30g, methanol 30g are filtered after being cooled to 20 DEG C, obtain crystal.By resulting crystal internal pressure 1.1kPa's
Under decompression, inside temperature 70 DEG C drying 3 hours.
Each assay value of the crystal of the resulting alcohols indicated with above-mentioned general formula (2) is as follows.
The weight of resulting crystal: 29g (yield: 82%)；
HPLC purity: 99% (polymer content: 0.7%)；
YI value: 0.7.
2 > of < embodiment
It other than triethylene glycol dimethyl ether is changed to diethylene glycol dimethyl ether, reacts, stirs same as Example 1ly
After 4 hours, reaction solution is analyzed using HPLC.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 92%；
Polymer: 0.6%.
The sodium hydrate aqueous solution 30g of toluene 30g, 12 weight % are added into resulting reaction solution, it is small in 85 DEG C of stirrings 1
When after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, resulting result is expressed as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 97%；
Polymer: 0.6%.
3 > of < embodiment
Other than triethylene glycol dimethyl ether is changed to cyclohexanone, react same as Example 1ly, after stirring 6 hours,
Reaction solution is analyzed using HPLC.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 93%；
Polymer: 1.0%.
The sodium hydrate aqueous solution 30g of toluene 30g, 12 weight % are added into resulting reaction solution, it is small in 85 DEG C of stirrings 1
When after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, resulting result is expressed as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 97%；
Polymer: 1.0%.
4 > of < embodiment
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 12.0g
(0.137mol), methyl iso-butyl ketone (MIBK) 45g, is warming up to 120 DEG C, after stirring 6 hours at the same temperature, is analyzed using HPLC
Reaction solution.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 91%；
Polymer: 0.8%.
The sodium hydrate aqueous solution 30g of methyl iso-butyl ketone (MIBK) 45g, 12 weight % are added into resulting reaction solution, 90
DEG C stirring 3 hours after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, by resulting result table
Show as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 96%；
Polymer: 0.8%.
5 > of < embodiment
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 13.1g
(0.149mol), methyl isoamyl ketone 30g, is warming up to 130 DEG C, after stirring 5 hours at the same temperature, is analyzed using HPLC
Reaction solution.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 91%；
Polymer: 0.9%.
The sodium hydrate aqueous solution 30g of methyl isoamyl ketone 60g, 12 weight % are added into resulting reaction solution, 100
DEG C stirring 3 hours after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, by resulting result table
Show as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 96%；
Polymer: 0.9%.
6 > of < embodiment
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 13.1g
(0.149mol), diethylene glycol fourth methyl ether 45g, is warming up to 120 DEG C, after stirring 5 hours at the same temperature, is analyzed using HPLC
Reaction solution.It is as follows to analyze result.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 92%；
Polymer: 0.7%.
The sodium hydrate aqueous solution 30g of toluene 60g, 12 weight % are added into resulting reaction solution, it is small in 85 DEG C of stirrings 3
When after stand, isolate water phase.Resulting organic phase is analyzed using HPLC, resulting result is expressed as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 97%；
Polymer: 0.7%.
1 > of < comparative example
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 13.1g
(0.149mol) and toluene 60.0g, is warming up to 115 DEG C, after stirring 5 hours at the same temperature, is analyzed instead using HPLC
Liquid is answered, as a result, remain 9 as raw material, 9 '-bis- (4- hydroxyl -3- phenyl) fluorenes.Thus, suitably
Continue to stir at the same temperature while analyzing reaction solution using HPLC, until inspection does not measure raw material 9,9 '-bis- (4- hydroxyls
Base -3- phenyl) fluorenes, as a result, not measuring 9,9 '-bis- (4- hydroxyls by examining at the time of 18 hours after heating
Base -3- phenyl) fluorenes.The analysis result based on HPLC after stirring 18 hours is as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 85%；
Polymer: 3.4%.
The sodium hydrate aqueous solution 30g of toluene 30g, 12 weight % are added into resulting reaction solution, it is small in 85 DEG C of stirrings 3
When, however the raising of purity is not observed, therefore interrupt stirring, and toluene 180g is added, is stirred 30 minutes at 80~85 DEG C, it is quiet
It postpones, isolates water phase.Resulting organic phase is analyzed using HPLC, resulting result is expressed as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 85%；
Polymer: 3.4%.
2 > of < comparative example
It other than toluene is changed to dimethylbenzene, is allowed to react identically as comparative example 1, as a result, until detection
9 as raw material are not gone out, 9 '-bis- (4- hydroxyl -3- phenyl) fluorenes need 20 hours.Stirring 20 hours after based on
The analysis result of HPLC is as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 84%；
Polymer: 3.5%.
3 > of < comparative example
It other than toluene is changed to chlorobenzene, is allowed to react identically as comparative example 1, as a result, until detecting not
9 as raw material out, 9 '-bis- (4- hydroxyl -3- phenyl) fluorenes need 14 hours.Stirring 14 hours after based on HPLC
Analysis result it is as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 86%；
Polymer: 2.5%.
4 > of < comparative example
It other than toluene is changed to cyclopentyl-methyl ether, is allowed to react identically as comparative example 1, as a result, directly
9 as raw material are not measured to inspection, 9 '-bis- (4- hydroxyl -3- phenyl) fluorenes need 14 hours.After stirring 14 hours
Analysis result based on HPLC is as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: it is not detected；
The alcohols indicated with above-mentioned general formula (2): 86%；
Polymer: 2.4%.
5 > of < comparative example
Into the glass system reactor for having blender, heating cooler and thermometer, 9,9 '-bis- (4- hydroxyls are added
Base -3- phenyl) fluorenes 30g (0.06mol), potassium carbonate 0.7g (0.005mol), ethylene carbonate 13.1g
(0.149mol) and acetone 30.0g, is warming up to 60 DEG C, stirs 5 hours at the same temperature, however inspection is not measured with above-mentioned
The alcohols that general formula (2) indicates, therefore interrupted reaction.The analysis result based on HPLC after stirring 5 hours is as follows.
9,9 '-bis- (4- hydroxyl -3- phenyl) fluorenes: 95%；
The alcohols indicated with above-mentioned general formula (2): it is not detected；
Polymer: it is not detected.
Claims (3)
1. a kind of manufacturing method of alcohols is the manufacturing method of the alcohols indicated with the following general formula (2),
In formula, R1And R2It is identical or different respectively, indicate halogen atom, alkyl or alkoxy；n1And n2Identical or different, table respectively
Show 0 or 1~3 integer；R3And R4It is identical or different respectively, indicate the alkylidene optionally with branch of carbon atom number 2~4；
The manufacturing method is in the presence for being selected from least one of the ketone of diol bisether and carbon atom number 4~12 compound
Under, react the phenol indicated with the following general formula (1) with alkylene carbonate esters,
In formula, R1、R2、n1、n2Meaning it is as described above.
2. the manufacturing method according to claim 1, wherein
Reaction temperature is 110 DEG C~135 DEG C.
3. manufacturing method according to claim 1 or 2, further include:
After the reaction, water and strong alkaline substance and mixed process are added into reaction product.
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| PCT/JP2017/019608 WO2017208973A1 (en) | 2016-05-30 | 2017-05-25 | Method for producing alcohol having fluorene backbone |
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| JP7358696B2 (en) * | 2018-09-19 | 2023-10-11 | 本州化学工業株式会社 | Crystalline mixture of bisfluorene compounds |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255609A (en) * | 1996-03-21 | 1997-09-30 | Taoka Chem Co Ltd | Production of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene |
| JP2009155252A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Alcohol having fluorene skeleton |
| JP2009155254A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
| JP2009173647A (en) * | 2007-12-26 | 2009-08-06 | Osaka Gas Co Ltd | Bifunctional (meth)acrylate having fluorene skeleton |
| JP2014227388A (en) * | 2013-05-24 | 2014-12-08 | 田岡化学工業株式会社 | Production method of binaphthalene compound |
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| JP6247992B2 (en) | 2014-04-17 | 2017-12-13 | 株式会社ダイセル | Method for producing halogen compound |
| JP2016138071A (en) * | 2015-01-29 | 2016-08-04 | 田岡化学工業株式会社 | Method for producing bis hydroxyethyl ether of bisphenols |
| JP6739136B2 (en) * | 2015-07-08 | 2020-08-12 | 田岡化学工業株式会社 | Crystal of alcohol having fluorene skeleton and method for producing the same |
| JP6739137B2 (en) * | 2015-07-21 | 2020-08-12 | 田岡化学工業株式会社 | Crystal of alcohol having fluorene skeleton and method for producing the same |
| JP6537388B2 (en) * | 2015-07-23 | 2019-07-03 | 田岡化学工業株式会社 | Inclusion compound using alcohols having a fluorene skeleton |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255609A (en) * | 1996-03-21 | 1997-09-30 | Taoka Chem Co Ltd | Production of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene |
| JP2009155252A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Alcohol having fluorene skeleton |
| JP2009155254A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
| JP2009173647A (en) * | 2007-12-26 | 2009-08-06 | Osaka Gas Co Ltd | Bifunctional (meth)acrylate having fluorene skeleton |
| JP2014227388A (en) * | 2013-05-24 | 2014-12-08 | 田岡化学工業株式会社 | Production method of binaphthalene compound |
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| JP7290908B2 (en) | 2023-06-14 |
| JP2017214364A (en) | 2017-12-07 |
| TW201808869A (en) | 2018-03-16 |
| CN109195936B (en) | 2022-02-11 |
| TWI707839B (en) | 2020-10-21 |
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