CN108884039A - The manufacturing method of novel dihydroxy compounds - Google Patents
The manufacturing method of novel dihydroxy compounds Download PDFInfo
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- CN108884039A CN108884039A CN201780020587.4A CN201780020587A CN108884039A CN 108884039 A CN108884039 A CN 108884039A CN 201780020587 A CN201780020587 A CN 201780020587A CN 108884039 A CN108884039 A CN 108884039A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Abstract
Project of the invention is to provide the manufacturing method of the novel dihydroxy compounds with indoline skeleton.Method by making N- phenylisatin compound shown in the following general formula (2) manufacture dihydroxy compounds shown in general formula (1) and reaction with benzene oxygen alcoholic compound shown in the following general formula (3), can solve the above subject.(in formula, R indicates the alkylidene of carbon atom number 2 to 6, R1、R2To each independently represent the alkyl of carbon atom number 1 to 8 or the alkoxy of carbon atom number 1 to 8, m indicates that 0 to 3 integer, n indicate 0 to 2 integer, wherein R when m is 2 or more1It may be the same or different, R when n is 22It may be the same or different).(in formula, R2, n be R with general formula (1)2, n it is identical).(in formula, R, R1, m be R, R with general formula (1)1, m it is identical).
Description
Technical field
The present invention relates to the manufacturing methods of novel dihydroxy compounds.
Background technique
In the past, double benzene oxygen alcohols (hydrogen atom of the hydroxyl of bisphenols is substituted by the compound of hydroxy alkyl) were used for poly- carbon
The thermosetting resins raw materials such as the thermoplastic synthetic resins such as acid ester resin raw material, epoxy resin, antioxidant raw material, thermosensitive recording body
The purposes such as raw material, photoresists raw material are in recent years higher and higher to performance required by these double benzene oxygen alcohols.
It has been known that there is bis- (4- (the 2- '-hydroxyethoxies of 3,3- with N- phenyl isoindoline skeleton for such a double benzene oxygen alcohols
Base) phenyl) -2- phenyl benzyl first lactams (non-patent literature 1).In addition, it has been known that there is by bis-phenol for the manufacturing method of double benzene oxygen alcohols
Compound is reacted with alkylene carbonate esters or alkylene oxides and the method that manufactures, but the monohydroxy in this method, as intermediary
Double benzene oxygen alcohols of alcoxyl matrix or target product can further be reacted with alkylene carbonate esters or alkylene oxides, generate hydroxyl alkane
The compound that the hydroxyl of oxygroup is further replaced by hydroxy alkoxy base, reduces reaction selectivity.In addition, there is fragrance because existing
The raw material or intermediary of race's property hydroxyl, therefore resulting compound can colour and thermal stability is poor, therefore be intended to use as optical applications
When need to repeat refine, industrially more unfavorable (non-patent literature 1, patent document 1).
Other manufacturing methods, just as bis- (4- (the 2- '-hydroxyethoxies of 9,9- with the compound for blocking more (cardo) construction
Base) phenyl) fluorenes manufacturing method for, it is known that the method for reacting Fluorenone with phenoxetol, but compared to phenol, benzene oxygen
Base ethyl alcohol class reactivity is low, records in patent document 2：In the bisphenols that the dehydrating condensation by phenol and ketone carries out
In manufacture, hydrogen chloride gas, cation exchange resin, solid acid for using generally as catalyst etc. do not show activity completely.
Therefore it has been known that there is the methods for reacting Fluorenone class with phenoxetol class in the presence of sulfuric acid or heteropolyacid catalyst
(patent document 3,4).But if using sulfuric acid as catalyst, sulfuric acid can be remained in product, and there are the form and aspect of product to dislike
The worry of change.In addition, when using heteropoly acid as catalyst, it is necessary to reaction temperature is set as high temperature, therefore reaction selectivity reduces,
It needs to react with substantially excessive phenoxetol class in order to improve reaction selectivity, and inefficiency.
Additionally, it is known that being manufactured with reacting for phenol with N- phenyl isoindoline by N- phenylphthalimide
The method (patent document 5) of bis- (4- the hydroxy phenyl) -2- phenyl benzyl first lactams of the 3,3- of skeleton.
But it in the compound with N- phenyl isoindoline skeleton or N- Phenylindole quinoline skeleton, then has not known
There is the manufacturing method that double benzene oxygen alcohols are manufactured by the condensation reaction of identical ketone and benzene oxygen alcohols.
Prior art document
Non-patent literature
Non-patent literature 1：Izvestiya Akademii Nauk Gruzinskoi SSR,Seriya
Khimicheskaya,1985,vol.11,p.78-80。
Patent document
Patent document 1：Japanese Unexamined Patent Publication 09-255609 bulletin；
Patent document 2：Japanese Unexamined Patent Publication 2000-191577 bulletin；
Patent document 3：Japanese Unexamined Patent Publication 07-165657 bulletin；
Patent document 4：Japanese Unexamined Patent Publication 2007-023016 bulletin；
Patent document 5：International Publication No. 2015/107467.
Summary of the invention
Problems to be solved by the invention
The present invention is completed by background of above situation, and project is to provide a kind of high-fire resistance, high refractive index
The manufacturing method of novel dihydroxy compounds with indoline skeleton.
Means for solving the problems
The inventors of the present invention discussion have indoline skeleton dihydroxy compounds manufacturing method, as a result, it has been found that compared to
Past reaction, by carrying out condensation reaction, reactivity using N- phenylisatin compound and benzene oxygen alcoholic compound as starting material
Higher, further, which carries out condensation reaction under conditions of more previous method is more mild, therefore for as high-quality
It measures the manufacturing method of dihydroxy compounds and is industrial advantageous approach, so as to complete the present invention.
The present invention is as described below.
1. the manufacturing method of dihydroxy compounds shown in a kind of general formula (1), to make N- phenyl shown in the following general formula (2)
Isatin compound is reacted with benzene oxygen alcoholic compound shown in the following general formula (3),
(in formula, R indicates the alkylidene of carbon atom number 2 to 6, R1、R2For the alkane for each independently representing carbon atom number 1 to 8
The alkoxy of base or carbon atom number 1 to 8, m indicate that 0 to 3 integer, n indicate 0 to 2 integer, wherein R when m is 2 or more1It can
It is identical or different, R when n is 22It may be the same or different).
(in formula, R2, n be R with general formula (1)2, n it is identical).
(in formula, R, R1, m be R, R with general formula (1)1, m it is identical)
Invention effect
With previously known card more construct raw material ketone compared with the reactivity of benzene oxygen alcoholic compound, through the invention and
The manufacturing method of the dihydroxy compounds obtained is especially a height of with the reactivity of N- phenylisatin compound and benzene oxygen alcoholic compound
The manufacturing method of advantage.
In addition, the reactivity because of N- phenylisatin compound and benzene oxygen alcoholic compound is high, if therefore with same reaction conditions into
Row compares, then compared with previous reaction, can be reacted with high yield and/or high conversion or can shorten the reaction time, and
And reacted in a mild condition, therefore industrial advantageous manufacturing method can be become.
Further, the manufacturing method of the present invention, which can get, is practically free of the high-purity dihydroxy compounds of impurity, pretend for
Industrially preparing process is useful.
Specific embodiment
The present invention described further below.
Dihydroxy compounds of the invention is shown in the following general formula (1)：
(in formula, R indicates the alkylidene of carbon atom number 2 to 6, R1、R2For the alkane for each independently representing carbon atom number 1 to 8
The alkoxy of base or carbon atom number 1 to 8, m indicate that 0 to 3 integer, n indicate 0 to 2 integer, wherein R when m is 2 or more1It can
It is identical or different, R when n is 22It may be the same or different).
In above-mentioned general formula (1), R is each independently the alkylidene of carbon atom number 2 to 6, and alkylidene can specifically illustrate
Such as Asia 1,2- second diyl, 1,2- propane diyl, 1,3- propane diyl, pentamethylene, hexa-methylene etc., but preferably carbon atom number
2 to 4 straight-chain or branched alkylidene, the particularly preferably alkylidene of carbon atom number 2 or 3.Illustrate above-mentioned general formula (1) herein
In "-O-R-OH " shown in hydroxy alkoxy base, be bonded to the hydroxyl of alkylidene R bonding position be not bonded to it is straight with ether
Connect the carbon atom (1 carbon atom) of the composition alkylidene R of bonding.When R is the alkylidene of 3 or more carbon atom, the bonding position of hydroxyl
The two or three-digit of preferably alkylidene " R " is set, wherein more preferably 2.It can specifically illustrate such as 2- hydroxyl-oxethyl, 2- hydroxyl
Base propoxyl group, 2- hydroxyl -1- methyl ethoxy, 3- hydroxy propyloxy group etc..
R1、R2It is each independently the alkyl of carbon atom number 1 to 8, the alkoxy of carbon atom number 1 to 8, R1For carbon atom number 1
To 8 alkyl when, alkyl is preferably the straight-chain or branched-chain alkyl of carbon atom number 1 to 4, can specifically illustrate as methyl,
Ethyl, n-propyl, isopropyl, isobutyl group etc..In the range of not undermining effect of the present invention, such a alkyl can have for example
The substituent groups such as phenyl, alkoxy.
In addition, R1、R2For carbon atom number 1 to 8 alkoxy when, alkoxy be preferably carbon atom number 1 to 4 straight-chain or
Branched alkoxy, can specifically illustrate such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy.Do not undermining the present invention
Effect in the range of, such a alkoxy can have the substituent group such as phenyl, alkoxy.
Preferred R1、R2For methyl.
In addition, in above-mentioned general formula (1), m 0,1,2 or 3, preferably 0,1 or 2, particularly preferably 0 or 1.Above-mentioned general formula
(1) in, n 0,1 or 2, preferably 0 or 1, particularly preferably 0.
In addition, replacing in above-mentioned general formula (1) about with the phenyl of the 3 of indoline skeleton carbon atom Direct Bondings
"-O-R-OH " base and R1The position of substitution, firstly, "-O-R-OH " base preferably relative to 3 carbon with indoline skeleton
Replaced for the phenyl carbon atom of atom Direct Bonding in 4 or 2, is more preferably replaced at 4.
In addition, R1Preferably for above-mentioned "-O-R-OH " base ortho position or contraposition replaced, when relative to
"-O-R-OH " base is in 4 substitutions for the phenyl carbon atom of 3 carbon atom Direct Bondings of the indoline skeleton, preferably
Replaced in 3 or 5, when "-O-R-OH " base is in 2 substitutions, is preferably replaced in 3 or 5.
In addition, when m is 2, R1The position of substitution be preferably：Relative to direct with 3 carbon atoms of aforementioned indoline skeleton
For the phenyl carbon atom of bonding, "-O-R-OH " base carries out substitution and R at 41Replaced at 3 and 5 or "-O-R-
OH " base carries out substitution and R at 41Replaced in 2 and 5.
Further, when m is 3, R1The position of substitution be preferably：Relative to straight with 3 carbon atoms of aforementioned indoline skeleton
For connecing the phenyl carbon atom of bonding, "-O-R-OH " base carries out substitution and R at 41Replaced at 2,3 and 5.
Therefore, dihydroxy compounds shown in above-mentioned general formula (1) is preferably the following general formula (4) compound represented：
(in formula, R2, n and general formula (1) R2, n it is identical, R3Each independently represent the alkane of hydrogen atom, carbon atom number 1 to 8
The alkoxy of base or carbon atom number 1 to 8, R4Each independently represent the alkyl of hydrogen atom or carbon atom number 1 to 4, wherein each
The R that a hydroxyl-oxethyl is replaced4Carbon atom number add up to 4 or less).
In above-mentioned general formula (4), R2, n preference or concrete example be R with general formula (1)2, n preference or concrete example phase
Together.
In addition, in above-mentioned general formula (4), R3For carbon atom number 1 to 8 alkyl or carbon atom number 1 to 8 alkoxy when,
The R of preference or concrete example and general formula (1)1For carbon atom number 1 to 8 alkyl or carbon atom number 1 to 8 alkoxy when it is identical.
Preferred R3For hydrogen atom, methyl.As preferred combination, relative to 3 carbon atom Direct Bondings with indoline skeleton
Phenyl carbon atom, 3 and 5 R3Preferably at least one is hydrogen atom, in addition, relative to 3 with indoline skeleton
The phenyl carbon atom of carbon atom Direct Bonding, 2 and 5 R3Preferably hydrogen atom.In addition, particularly preferably R3All hydrogen
Atom.
In above-mentioned general formula (4), R4For carbon atom number 1 to 4 alkyl when, can specifically illustrate such as methyl, ethyl, positive third
Base etc..
Wherein, R4Preferably hydrogen atom or methyl.
Dihydroxy compounds shown in general formula (1) of the invention can specifically illustrate such as：Bis- (4- (the 2- hydroxyl second of 3,3-
Oxygroup) phenyl) -1- phenyl -1H- indol-2-one；
Bis- (4- (2- hydroxy-2-methyl ethyoxyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl -1- methyl ethoxy) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) -3- the aminomethyl phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (3- ethyl -4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) -3,5- the 3,5-dimethylphenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) -2,5- the 3,5-dimethylphenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) -2,3,5- the trimethylphenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (2- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (2- (2- hydroxyl-oxethyl) -3- the aminomethyl phenyl) -1- phenyl -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) phenyl) -1- (4- the aminomethyl phenyl) -1H- indol-2-ones of 3,3-；
Bis- (4- (2- hydroxyl-oxethyl) phenyl) -1- (2- the aminomethyl phenyl) -1H- indol-2-ones of 3,3-；And
Bis- (4- (2- hydroxyl-oxethyl) phenyl) -1- (4- methoxyphenyl) -1H- indol-2-ones of 3,3- etc..
In the manufacturing method of dihydroxy compounds shown in general formula (1) of the invention, one of raw material is the following general formula (2) institute
The N- phenylisatin compound shown：
(in formula, R2, n be R with general formula (1)2, n it is identical).
R2, n preference or the concrete example also R with general formula (1)2, n preference or concrete example it is identical.
N- phenylisatin compound shown in such a above-mentioned general formula (2) can specifically illustrate such as：
1- phenyl -1H- indoles -2,3- diketone；
1- (4- aminomethyl phenyl) -1H- indoles -2,3- diketone；
1- (2- aminomethyl phenyl) -1H- indoles -2,3- diketone；And
1- (4- methoxyphenyl) -1H- indoles -2,3- diketone etc..
Another raw material is benzene oxygen alcoholic compound shown in the following general formula (3)：
(in formula, R, R1, m be R, R with general formula (1)1, m it is identical).
R、R1, m preference or concrete example also R, R with general formula (1)1, m preference or concrete example it is identical.
Benzene oxygen alcoholic compound shown in such a above-mentioned general formula (3) is preferably general formula (6) compound represented：
(in formula, R3、R4For the R with general formula (4)3、R4It is identical).
R3、R4Preference or the concrete example also R with general formula (4)3、R4Preference or concrete example it is identical.
Such a above-mentioned general formula (6) compound represented can specifically illustrate such as：
2- phenoxetol；
2- phenoxypropanol；
1- phenoxy group -2- propyl alcohol；
2- (2- methylphenoxy) ethyl alcohol；
2- (2- ethyl phenoxy group) ethyl alcohol；
2- (2,6- dimethyl phenoxy) ethyl alcohol；
2- (2,5- dimethyl phenoxy) ethyl alcohol；And
2- (2,3,6- trimethylbenzene oxygroup) ethyl alcohol etc..
The manufacturing method that the present invention will be described in detail, that is, make N- phenylisatin compound shown in general formula (2) and general formula (3)
Shown in benzene oxygen alcoholic compound reaction, and manufacture have indoline skeleton general formula (1) shown in dihydroxy compounds method.
Condensation reaction is generally to make above-mentioned N- phenylisatin compound and benzene oxygen alcoholic compound anti-in presence of an acid catalyst
It answers and carries out.Firstly, reacting N- phenylisatin compound and benzene oxygen alcoholic compound in presence of an acid catalyst, with alkali neutralization institute
After obtaining reaction mixture, according to known method partial crystallization, filtering, and 1 partial crystallization filtrate is obtained.
When reaction, as long as the addition molar ratio of the benzene oxygen alcoholic compound relative to N- phenylisatin compound is theoretical value
(2.0) it more than, is then not particularly limited, but it is preferable to use more than 3.0 times of moles, the model of more preferably 3.5 to 20 times moles
It encloses, the range of particularly preferred 4.0 to 15 times of moles.
Acid catalyst can illustrate such as hydrochloric acid, hydrogen chloride gas, 60 to 98% sulfuric acid, 85% phosphoric acid inorganic acid；To toluene
The organic acids such as sulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid or trifluoroacetic acid；Heteropoly acid, ion exchange resin, activity are glutinous
Solid acids such as soil, silica-alumina etc..Preferably hydrogen chloride gas.The suitable usage amount of such a acid catalyst
It is different and different because of reaction condition, but for example, hydrogen chloride gas when, can be by inert gases such as nitrogen to reaction system
After the air of system is replaced, be blown into hydrogen chloride gas, make chlorine hydride gas concentration in reaction vessel in gas phase become 75 to
100 capacity %, and the hydrogen cloride concentration in reaction solution is made to become saturated concentration.When for 35% hydrochloric acid, relative to benzene oxygen alcohol compound
100 parts by weight of object are used, preferably the range of 10 to 40 parts by weight, more preferably 20 to 30 weights with the range of 5 to 70 parts by weight
Measure the range of part.Here, sulfuric acid can remain in purpose compound, therefore have chemical combination if using sulfuric acid as acid catalyst
The worry that the form and aspect of object deteriorate, in addition, using heteropoly acid as when acid catalyst, it is necessary to reaction temperature is set as high temperature, therefore instead
It can should selectively reduce, and inefficiency.
When reaction, optionally cocatalyst can be used together with acid catalyst.Such as use hydrogen chloride gas as
When catalyst, use thio-alcohol as cocatalyst, thus can accelerate reaction speed.Such a thio-alcohol can enumerate alkyl
Mercaptan carboxylic acid's class of thio-alcohol, mercaptan carboxylic acid's class, preferably the alkyl sulfide alcohols of carbon atom number 1 to 12, carbon atom number 1 to 12,
It can enumerate such as methyl mercaptan, ethanethio, n octylmercaptan, n-laurylmercaptan, the alkali metal of the classes such as their sodium salt
Salt, thioacetic acid, thioacetic acid, β-mercaptopropionic acid etc..
In addition, these to may be used alone or in combination two types used above.
Relative to the N- phenylisatin compound of raw material, thio-alcohol usage amount as cocatalyst usually with 0.5 to
The range of 20 moles of % uses, the range of preferably 2 to 10 moles %.
In addition, when reaction, about reaction dissolvent, as long as the N- phenylisatin compound of raw material and benzene oxygen alcoholic compound
Fusing point is low and operational no problem, then need not use solvent, but to improve the reasons such as operability, reaction speed when industrial production
For can also be used.As long as reaction dissolvent does not distillate from reactor in reaction temperature and is inertia to reaction, without especially limit
System, but can illustrate such as toluene, dimethylbenzene aromatic hydrocarbon；The aliphatic alcohols such as methanol, normal propyl alcohol, isobutanol；Hexane, heptane, ring
The aliphatic hydrocarbons such as hexane；The carboxylic acid esters such as ethyl acetate, butyl acetate or their mixture.Rouge is preferably used in these
Fat race alcohol.
In addition, can optionally be added few to reduce the freezing point of benzene oxygen alcoholic compound and promote the reaction of acid catalyst
Measure water.When especially acid catalyst is hydrogen chloride gas, because water can promote the absorption of the hydrogen chloride gas of catalyst, therefore it is preferred that.Add
When adding water, relative to 100 parts by weight of benzene oxygen alcoholic compound, the additive amount of water is preferably the range of 0.5 to 15.0 parts by weight.
Reaction temperature is different due to the conditions such as the catalyst that uses, but preferably 20 to 70 DEG C of range, more preferably 30 to
60 DEG C of range.Reaction pressure is usually to carry out under normal pressure, but according to the boiling point of workable organic solvent, can also pressurize
Or the lower progress of decompression is so that reaction temperature becomes in aforementioned range.If being reacted under the conditions of such a, reaction is usual
Terminated at 1 to 30 hour or so.
Reaction end can be confirmed by liquid chromatography or gas chromatographic analysis.Preferably with unreacted N- phenylisatin
Object is closed to disappear and can not confirm that target product increased time point is reaction end.
Reaction yield relative to benzene oxygen alcoholic compound is usually 75 to 95 moles of % or so.
After reaction, the aqueous slkalis such as ammonium hydroxide, sodium hydrate aqueous solution are added into resulting reaction mixture to neutralize
Acid catalyst, and obtaining the reaction containing dihydroxy compounds shown in general formula (1) of the invention terminates mixed liquor.
After the reaction mixture of neutralization optionally to be passed through to the unreacted benzene feedstock oxygen alcoholic compound of distillation removal, added
Enter water and water-insoluble organic solvents and the washing process for being sufficiently stirred and separating oil reservoir.Used organic solvent need to be at this time
It can dissolve the dihydroxy compounds of general formula (1), and the organic solvent small to the solubility of water.As organic molten with the property
It is aromatic hydrocarbon that toluene, dimethylbenzene etc. can be used in agent；The aliphatic hydrocarbons such as hexamethylene, normal heptane；The fat such as methyl iso-butyl ketone (MIBK)
Race's ketone；The alcoholic solvents such as butanol.
It is after optionally partial solvent being removed with resulting organic solvent layer after washing among the above with distillation, this is organic
Solvent layer is directly cooling or is temporarily heated as uniform solution, and cooling or suitable addition partial crystallization solvent and poor solvent are simultaneously cold
But, when crystallization is thus precipitated, the crystallization is filtered, thus can get crude or high-purity target product.
Above-mentioned resulting target product can further use solvent and be recrystallized and be refined.It is organic molten used at this time
Agent can enumerate the aromatic hydrocarbon solvents such as toluene, dimethylbenzene, mesitylene；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), hexamethylene
The ketone solvents such as ketone；And the ester solvents such as ethyl acetate, butyl acetate；The alcoholic solvents such as butanol, these can be used alone or use 2 types
Above mixture.
Operate, and be after the completion of reaction concentrated under reduced pressure reaction dissolvent etc. instead of above-mentioned partial crystallization, and by its residue with
The purification such as col-umn chromatography, thus can get high-purity product.
Here, the impurity that dihydroxy compounds shown in general formula (1) may contain can be enumerated shown in the following general formula (7)
(hydroxyl of hydroxy alkoxy base is further by hydroxyl alkane for more EO bodies shown in 1EO body (monohydroxy alcoxyl matrix), the following general formula (8)
The compound that oxygroup replaces).But manufacturing method through the invention and make N- phenylisatin compound shown in general formula (2)
It is reacted with benzene oxygen alcoholic compound shown in general formula (3) to manufacture dihydroxy compounds shown in general formula (1), thus can manufacture and be free of
Dihydroxy shown in the general formula (1) of the impurity of more EO bodies shown in 1EO body shown in the following general formula (7) or the following general formula (8)
Close object.
Above-mentioned 1EO body is shown in the following general formula (7)：
(in formula, R, R1、R2, m, n be R, R with general formula (1)1、R2, m, n it is identical).
R、R1、R2, m, n preference or concrete example also R, R with general formula (1)1、R2, m, n preference or concrete example phase
Together.
Above-mentioned more EO bodies are shown in the following general formula (8)：
(in formula, R, R1、R2, m, n and general formula (1) R, R1、R2, m, n it is identical, k each independently represents 1 to 5 integer,
Wherein, by k simultaneously be 1 the case where except).
R、R1、R2, m, n preference or concrete example also R, R with general formula (1)1、R2, m, n preference or concrete example phase
Together.
In more EO bodies shown in above-mentioned general formula (8), as containing a possibility that higher compound 3EO body be following logical
Shown in formula (9)：
(in formula, R, R1、R2, m, n be R, R with general formula (1)1、R2, m, n it is identical).
R、R1、R2, m, n preference or concrete example also R, R with general formula (1)1、R2, m, n preference or concrete example phase
Together.
Compared with previous manufacturing method, the manufacturing method of the present invention reactivity is high, therefore can be under mild reaction conditions
It is reacted, and compared with previous reaction, the dihydroxy compounds as target can be obtained using high yield and/or high conversion.
In addition, the dihydroxy compounds as shown in the resulting general formula of the manufacturing method of the present invention (1) be without：With above-mentioned
The impurity of 1EO body, more EO bodies that 3EO body is representative, and it is high-purity, therefore in optical characteristics sides such as thermal stability, product form and aspect
Face is excellent.
The dihydroxy compounds as shown in the resulting general formula of the manufacturing method of the present invention (1) is high-purity, therefore it can be expected that tool
There are a high-fire resistance, high refractive index, especially it can be expected that excellent effect in terms of optical material polycarbonate.That is, by being set as
High-molecular-weight polycarbonate keeps the transparency, heat resistance, mechanical property, impact resistance, mobility etc. excellent, it can be expected that making
For optical applications such as CD, lens, or it can be expected that automotive field, electrical/electronic field, each is used in as engineering plastics
The various fields such as kind container.
In addition, when polycarbonate oligomer can be used as through various polymerizations manufacture high-molecular-weight polycarbonate
Raw material, also widely available surface modifier, fire retardant, ultraviolet absorbing agent, mobility modifying agent, plasticiser, the resin made closes
The additive of the polymer modifiers such as golden expanding material etc..
In addition, being the hydroxyl using end by the resulting dihydroxy compounds of the invention of the manufacturing method of the present invention, remove
Other than polycarbonate, also it can be expected that be used as epoxy resin, oxetane resin, acrylic resin, polyester, polyarylate,
It is the resin raw materials such as polyether-ether-ketone, polysulfones, novolaks, bakelite (resol), other light-sensitive composition raw materials, against corrosion
Agent addition agent, color developing agent, antioxidant.
Especially it can be expected that dihydroxy compounds of the invention and acrylic acid etc. is made to react and obtain diacrylate etc., as
The utilization of acrylic monomers or acrylic resin raw material, and it can be expected that as optical hard coating material made of these has been used
Use.
Embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to these embodiments.
In addition, softening point, refractive index in embodiment, purity measure by the following method.
[analysis method]
1. softening point measurement
Device：Shimadzu Scisakusho Ltd (Zhu formula Hui She Island Jin System makees institute) DSC-60 DIFFERENTIAL processed
SCANNING CALORIMETER。
Elevated Temperature Conditions：10 DEG C/min (30 DEG C → 200 DEG C).
Atmosphere gas：Nitrogen (flow：50ml/ minutes).
Measuring method：
The 1st measurement is carried out with above-mentioned Elevated Temperature Conditions, and fusing point is measured by its wave crest that absorbs heat.
Same sample is cooled to room temperature to thereafter and is carried out under the same conditions the 2nd measurement, is soft with its wave crest that absorbs heat
Change point.
2. detecting refractive index
Device：Capital of a country electronics industry Co., Ltd. (capital of a country Electricity Industrial Co., Ltd) Refractometer RA- processed
500N。
Measuring method：
The THF solution (THF refractive index 1.40) for preparing concentration 10,15,30%, by extrapolation by the refractive index of the solution
Calculate the refractive index of measurement compound.
3. purity testing
Device：Shimadzu Scisakusho Ltd CLASS-LC10.
Pump：LC-10ATvp.
Column oven：CTO-10Avp.
Detector：SPD-10Avp.
Tubing string：Shim-pack CLC-ODS internal diameter 6mm, length 150mm.
Oven temperature：50℃.
Flow：1.0ml/min.
Mobile phase：(A) methanol, (B) 0.2vol% acetic acid aqueous solution.
Gradient condition：(A) volume % (time started away from analysis)
60% (0min) → 60% (20min) → 100% (40min) → 100% (50min)
Sample injection rate：20μl.
Detection wavelength：280nm.
1 > of < embodiment
The manufacture -1 of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-
2- phenoxetol 331.2g is added into the four-hole boiling flask for having thermometer, blender, cooling tube, and (2.40 rub
You), 1- phenyl -1H-Indole-2,3-dione 44.6g (0.20 mole), after being replaced with nitrogen to reaction vessel, blown in 40 DEG C
Enter hydrogen chloride gas, the chlorine hydride gas concentration in gas phase portion is made to become 95% or more.Thereafter it is water-soluble to add 15% methyl mercaptan sodium
Liquid 4.2g (methyl mercaptan sodium is 0.009 mole), is stirred 22 hours in 40 DEG C.
1- phenyl -1H-Indole-2,3-dione conversion ratio after reaction is 99.7%, 3,3- bis- (4- (2- hydroxyl second
Oxygroup) phenyl) reaction yield (relative to 1- phenyl -1H- indoles -2,3- diketone) of -1- phenyl -1H- indol-2-one is
93.7%.
After reaction, 16% sodium hydrate aqueous solution 304.5g (sodium hydroxide is 1.22 moles) is added, so that pH tune
Be made into is 6.Resulting solution is warming up to 150 DEG C, unreacted 2- phenoxy group second is removed with distillation under the decompression of 2.4kPa
After alcohol, toluene 268.3g is added.2 water washing operations are carried out, which is that water 45.0g is added into resulting solution, with
After 80 DEG C of stirrings, stands and remove water layer.After washing, resulting oil reservoir is warming up to 160 DEG C, to steam under the decompression of 1.0kPa
It evaporates except cooling after solvent, in 110 DEG C of addition toluene 582.2g and in 70 DEG C of addition methanol 72.3g.Thereafter, 30 DEG C are cooled to,
The crystallization of precipitation is filtered, thus to obtain the coarse crystallization 61.4g of white crystals.
N-butyl alcohol 226.5g is added to resulting coarse crystallization 55.5g, after 110 DEG C of dissolutions, under normal pressure to distill removal
After n-butyl alcohol 112.7g, 30 DEG C are cooled to, the crystallization of precipitation is filtered.By resulting crystallization under reduced pressure with 80 DEG C of dryings, by
This obtains bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-one 48.5g of 3,3-.
Proton NMR spectral (400MHz, solvent DMSO-D6, standard TMS)
Chemical shift (signal shape, proton number)：3.7ppm(m,4H),4.0ppm(t,4H),4.9ppm(t,2H),
6.7ppm (d, 1H), 6.9ppm (d, 4H), 7.1~7.2ppm (m, 5H), 7.3ppm (t, 1H), 7.4ppm (d, 1H), 7.5ppm
(m,3H),7.6ppm(t,2H)。
2 > of < embodiment
The manufacture -2 of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-
2- phenoxetol 34.8g is added into the four-hole boiling flask for having thermometer, blender, cooling tube, and (0.25 rubs
You), 1- phenyl -1H-Indole-2,3-dione 10.0g (0.045 mole), n octylmercaptan 0.35g (0.0024 mole), on one side
Temperature in system is held in 50 to 55 DEG C and adds methanesulfonic acid 20.7g on one side, is stirred 4.5 hours in 50 to 55 DEG C thereafter.
1- phenyl -1H-Indole-2,3-dione conversion ratio after reaction is 100%, 3,3- bis- (4- (2- '-hydroxyethoxies
Base) phenyl) reaction yield (relative to 1- phenyl -1H- indoles -2,3- diketone) of -1- phenyl -1H- indol-2-one is
85.3%, 3EO body shown in 1EO body and general formula (9) shown in general formula (7) is all detectable limit or less.
By the result of embodiment 1,2 it is found that confirmation the manufacturing method of the present invention is that can get to be practically free of shown in general formula (7)
1EO body or general formula (9) shown in 3EO body impurity high-purity dihydroxy compounds method, and using as industry
Manufacturing method.
In addition, the manufacturing method with reference to documented by Japanese Unexamined Patent Application Publication 2010-505011 bulletin etc., makes shown in general formula (2)
N- phenylisatin compound and oxybenzene compound reaction, then make resulting bisphenol compound and carbonic acid with indoline skeleton
The reaction such as alkylene carbonate, carries out hydroxy alkylated, and the method for manufacturing dihydroxy compounds shown in general formula (1) can not inhibit general formula
(7) generation of 3EO body impurity shown in 1EO body shown in or general formula (9), therefore the result is that high-purity dihydroxy chemical combination can not be obtained
Object.About this, illustrated in following " comparative examples 1 ".
1 > of < comparative example
The manufacture of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-
(process 1)
The manufacture of bis- (4- the hydroxy phenyl) -1- phenyl -1H- indol-2-ones of 3,3-
Phenol 225.9g (2.40 moles), 1- benzene are added into the four-hole boiling flask for having thermometer, blender, cooling tube
Base -1H-Indole-2,3-dione 44.6g (0.20 mole) after replacing with nitrogen to reaction vessel, is blown into hydrogen chloride in 40 DEG C
Gas makes the chlorine hydride gas concentration in gas phase portion become 95% or more.Thereafter it is stirred 22 hours in 30 DEG C.1- after reaction
Phenyl -1H-Indole-2,3-dione conversion ratio be 100%, 3,3- bis- (4- hydroxy phenyl) -1- phenyl -1H- indol-2-ones it is anti-
Product yield (relative to 1- phenyl -1H- indoles -2,3- diketone) is 88.8%.
After reaction, 16% sodium hydrate aqueous solution 57.4g (sodium hydroxide is 0.23 mole), 75% phosphoric acid are added
0.3g, water 3.0g, toluene 40.0g are warming up to 75 DEG C and stir.Thereafter, 30 DEG C are cooled to, the crystallization being precipitated is filtered, by
This obtains coarse crystallization 86.8g.
Toluene 151.9g, methyl ethyl ketone 325.5g, water 87.0g are added to resulting coarse crystallization, it is quiet after 70 DEG C of dissolutions
It sets and removes water layer.2 water washing operations of further progress, the water washing operations stand and go for addition water and after 70 DEG C of stirrings
Except water layer.After washing, resulting oil reservoir is warming up to 110 DEG C, adds toluene after removing solvent with distillation, be cooled to 30 DEG C and is incited somebody to action
The crystallization filtering being precipitated.By resulting crystallization under reduced pressure in 60 DEG C of dryings, thus to obtain bis- (4- the hydroxy phenyl) -1- of 3,3-
Phenyl -1H- indol-2-one 56.1g.
Purity 99.5% (high performance liquid chroma- tography area %)
Yield 71.3% (relative to 1- phenyl -1H- indoles -2,3- diketone)
300 DEG C of fusing point (Differential Scanning Calorimetry analysis)
(process 2)
The manufacture of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-ones of 3,3-
Bis- (the 4- hydroxy benzenes of the resulting 3,3- of process 1 are added into the four-hole boiling flask for having thermometer, blender, cooling tube
Base) -1- phenyl -1H- indol-2-one 40.0g (0.10 mole), n-butyl alcohol 60.0g, ethylene carbonate 26.0g (0.30 mole),
48% potassium hydroxide aqueous solution 0.60g (potassium hydroxide is 0.0051 mole), Tetrabutylammonium bromide 0.33g (0.0010 mole),
After being replaced with nitrogen to reaction vessel, is stirred while being maintained at 118 to 120 DEG C 12 hours, thereafter, adds water 5.1g,
It is futher stirred while being maintained at 105 to 107 DEG C 4 hours.
After 70 DEG C are added 10% acetic acid aqueous solution 12.7g to resulting reaction solution, addition methyl iso-butyl ketone (MIBK) 20.0g,
Water 40.0g stands after 80 DEG C of dissolutions and removes water layer.1 water washing operations of further progress, the water washing operations are addition water
And after stirring, stands and remove water layer.After washing, resulting oil reservoir is warming up to 126 DEG C, after removing solvent with distillation, addition
Toluene and water.25 DEG C are cooled to, the crystallization being precipitated is filtered, thus to obtain coarse crystallization 75.1g.
N-butyl alcohol 300.4g is added to resulting coarse crystallization, after 75 DEG C of dissolutions, is warming up to 120 DEG C, it is molten with distillation removal
After agent, 25 DEG C are cooled to, the crystallization being precipitated is filtered.By resulting crystallization under reduced pressure with 80 DEG C of dryings, thus to obtain 3,
Bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1- phenyl -1H- indol-2-one 31.5g of 3-.
2 > of < comparative example
The manufacture of 9,9- ((4- hydroxyl-oxethyl) phenyl) fluorenes
2- phenoxetol 78.3g is added into the four-hole boiling flask for having thermometer, blender, cooling tube, and (0.57 rubs
You), after replacing with nitrogen to reaction vessel, be blown into hydrogen chloride gas in 40 DEG C, make the chlorine hydride gas concentration in gas phase portion at
It is 98% or more.It, will be solubilized after being subsequently added into 21% methyl mercaptan sodium water solution 11.3g (methyl mercaptan sodium is 0.034 mole)
Solution instills for (0.28 mole) of 9-Fluorenone 50.0g cost 2 hours in 2- phenoxetol 75g (0.54 mole).It is stirred in 40 DEG C
After 30 hours, 9-Fluorenone conversion ratio is 27%, and 9,9- ((4- hydroxyl-oxethyl) phenyl) fluorenes reaction yields are 15%.
3 > of < comparative example
The manufacture of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -2- phenyl benzyl first lactams of 3,3-
2- phenoxetol 331.6g is added into the four-hole boiling flask for having thermometer, blender, cooling tube, and (2.40 rub
You), N- phenylphthalimide 44.8g (0.20 mole), after replacing with nitrogen to reaction vessel, be blown into chlorine in 40 DEG C
Change hydrogen, the chlorine hydride gas concentration in gas phase portion is made to become 95% or more.Thereafter, 15% methyl mercaptan sodium water solution is added
4.2g (methyl mercaptan sodium is 0.009 mole), is stirred 22 hours in 40 DEG C.
Bis- (4- (2- hydroxyl-oxethyl) the phenyl) -2- phenyl benzyls of 3,3- are not observed in the reaction solution after reaction 22 hours
The generation of first lactams.
Can be confirmed by the result of comparative example 2 and 3, compared to the reacting of 9-Fluorenone and 2- phenoxetol (comparative example 2) or
N- phenylphthalimide reacts (comparative example 3) with 2- phenoxetol, the general formula as the manufacturing method of the present invention
(2) reactivity of N- phenylisatin compound shown in and phenoxyethanol compound shown in general formula (3) is especially high.
That is, the reactivity of the raw material ketone and benzene oxygen alcoholic compound more constructed compared to previously known card, of the invention
The manufacturing method of dihydroxy compounds shown in general formula (1) is with the reactivity of N- phenylisatin compound and benzene oxygen alcoholic compound
The manufacturing method of especially a height of advantage.
The manufacturing method of the present invention be because the reactivity is high, and compared with previous known production method, can with high yield and/
Or high conversion is reacted or can shorten the reaction time, also, is reacted in temperate condition, therefore can become industrially has
The manufacturing method of benefit.
Further, the manufacturing method of the present invention, which can get, is practically free of the high-purity dihydroxy compounds of impurity, pretend for
Industrially preparing process is useful.
Claims (1)
1. a kind of manufacturing method of dihydroxy compounds shown in general formula (1), which is characterized in that make shown in the following general formula (2)
N- phenylisatin compound is reacted with benzene oxygen alcoholic compound shown in the following general formula (3),
In formula, R indicates the alkylidene of carbon atom number 2 to 6, R1、R2Alkyl or the carbon for each independently representing carbon atom number 1 to 8 are former
The alkoxy of subnumber 1 to 8, m indicate that 0 to 3 integer, n indicate 0 to 2 integer, wherein R when m is 2 or more1It can be identical or not
Together, R when n is 22It may be the same or different；
In formula, R2, n be R with general formula (1)2, n it is identical；
In formula, R, R1, m be R, R with general formula (1)1, m it is identical.
Applications Claiming Priority (3)
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| JP2016063776 | 2016-03-28 | ||
| JP2016-063776 | 2016-03-28 | ||
| PCT/JP2017/011627 WO2017170096A1 (en) | 2016-03-28 | 2017-03-23 | Method for producing novel dihydroxy compound |
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| JP (1) | JPWO2017170096A1 (en) |
| KR (1) | KR102408697B1 (en) |
| CN (1) | CN108884039A (en) |
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| WO (1) | WO2017170096A1 (en) |
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| WO2016014629A1 (en) * | 2014-07-22 | 2016-01-28 | Sabic Global Technologies B.V. | High heat monomers and methods of use thereof |
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| DE19638888A1 (en) * | 1996-09-23 | 1998-03-26 | Bayer Ag | Production of cyclic aromatic bis:phenol compounds |
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| JP5517022B2 (en) * | 2008-11-21 | 2014-06-11 | ナガセケムテックス株式会社 | Condensed ring structure-containing alcohol compound |
| KR101624374B1 (en) * | 2009-04-13 | 2016-05-25 | 타오카 케미컬 컴퍼니 리미티드 | Method for producing fluorene derivative |
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| JP6155999B2 (en) * | 2013-09-13 | 2017-07-05 | Jsr株式会社 | Resin molded body, film / lens, transparent conductive film, resin composition, polymer |
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- 2017-03-23 KR KR1020187029703A patent/KR102408697B1/en active IP Right Grant
- 2017-03-23 JP JP2018509160A patent/JPWO2017170096A1/en active Pending
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- 2017-03-23 CN CN201780020587.4A patent/CN108884039A/en active Pending
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| JP2001206863A (en) * | 2000-01-25 | 2001-07-31 | Osaka Gas Co Ltd | Fluorene compound and method for the same |
| CN101516967A (en) * | 2006-09-28 | 2009-08-26 | 拜尔材料科学股份公司 | Polycarbonates and copolycarbonates having improved adhesion to metals |
| JP2009256342A (en) * | 2008-03-27 | 2009-11-05 | Osaka Gas Co Ltd | Method for producing alcohol having fluorene skeleton |
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| JPWO2017170096A1 (en) | 2019-02-07 |
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| TWI718276B (en) | 2021-02-11 |
| KR20180128434A (en) | 2018-12-03 |
| KR102408697B1 (en) | 2022-06-13 |
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