CN108017521A - Double [6- (the 2- hydroxy ethoxies of the 9,9- of high-purity high-bulk-density）Naphthyl] fluorenes preparation method - Google Patents
Double [6- (the 2- hydroxy ethoxies of the 9,9- of high-purity high-bulk-density）Naphthyl] fluorenes preparation method Download PDFInfo
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- CN108017521A CN108017521A CN201711029609.1A CN201711029609A CN108017521A CN 108017521 A CN108017521 A CN 108017521A CN 201711029609 A CN201711029609 A CN 201711029609A CN 108017521 A CN108017521 A CN 108017521A
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- fluorenes
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- naphthyl
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- hydroxy ethoxies
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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
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is with polar aprotic solvent N, N dimethylacetylamides, N, N dimethylformamides, N methyl pyrrolidones, dimethyl sulfoxide, diglycol dimethyl ether, diglycol diethyl ether, triethylene-glycol dimethyl ether, triethylene-glycol diethyl ether, multicondensed ethylene glycol diformazan (or second) ether etc. are reaction promoter, in alkaline conditions 9,9 pairs of (2 hydroxynaphenyl) fluorenes and ethylene carbonate ester condensation prepare 9,9 pairs of [6 (2 hydroxy ethoxies of high-purity high-bulk-density）Naphthyl] fluorenes.Purity（HPLC）More than 99.0%；Bulk density is more than 0.4g/ cubic centimetres, loss on drying<0.5% (120 DEG C, 30min)；Melt absworption peak 213 222oC.X powder diffractions (XRPD) spectrum is 7.7 ± 0.2 with such as pattern of attached drawing 3 and with 2 θ values0,8.8±0.20,12.5±0.20,14.3±0.20,15.5±0.20,17.7±0.20,18.7±0.20,19.5±0.20,20.4±0.20,20.9±0.20,21.2±0.20,22.2±0.20,22.7±0.20,23.1±0.20,24.8±0.20,25.4±0.20,25.9±0.20,26.7±0.20Characteristic diffraction peak.
Description
Technical field
The preparation side of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of photoelectric material intermediate 9,9- of high-purity high-bulk-density
Method.
Background technology
9,9- double [6- (2- hydroxy ethoxies) naphthyl] fluorenes are the important intermediates of photoelectric material, by the epoxy of its derivative synthesis
Resin, polyester resin, polyacrylic resin, polyimides have that index of refraction is high, heat endurance is high and good transparency etc. is excellent
Benign matter, in light-emitting diode packaging material, photocon, bright enhancement film, light polarizing film, reflective membrane, optical mirror slip and electric lithography
Material etc. has important application.
Japan Patent JP5513825, JP2011068624, JP2016069643 and JP2016079405 report 9,9-
The preparation method of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes, the synthesis step and result of these patents are all identical.The synthetic method
Using the concentrated sulfuric acid as catalyst, 3- mercaptopropionic acids are co-catalyst, by 9-Fluorenone and 2- (naphthyl epoxide) ethanol in xylene solution
In 60 DEG C stirring reaction 5 it is small when, after reaction with 48% sodium hydroxide solution wash and repeatedly wash, products therefrom purity
(HPLC analyses) 98.3%, yield 67%, these Japan Patents do not report product 9, double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9-
Fusing point, crystal form and bulk density.This method consumes a large amount of sulfuric acid (sulfuric acid dosage is 4 times of moles of 9-Fluorenone).And need height
In concentration sodium oxide molybdena and wash, cause a large amount of spent acid contaminated wastewater environment.Big excessive 2- (naphthyl epoxide) ethanol is needed at the same time
Raw material (being more than 4 times of moles of 9-Fluorenone), recycling is difficult, and production cost is high.And double [6- (the 2- hydroxyl second of products obtained therefrom 9,9-
Epoxide) naphthyl] fluorenes yield is low, and purity is low (98%).
Japan Patent JP5330683, JP2009155253, JP2009173648, JP2011168721,
For JP2011168722 and JP2011168723 all using ethylene carbonate as hydroxyethylating agent, methylimidazole is alkali, in a contracting two
In 100 in ethylene glycol solvent oCMake double (2 hydroxy naphthalene base) the fluorenes hydroxyethylations of 9,9-.The synthesis step and result of these patents are all
It is identical.Reacting coarse product is obtained through recrystallisation from isopropanol, only obtains 61 grams of products from 1 mole of 9-Fluorenone synthesis, yield is only
11.3%.Purity 95.7%.Products obtained therefrom 9, double [6- (2- hydroxy ethoxies) naphthyl] the fluorenes yields of 9- are extremely low, and purity is low.While this
A little patents are also without report product 9, the fusing point of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9-, crystal form and bulk density.In order to gram
The shortcomings that taking above method, the present invention make the hydroxyl ethoxyl etherification of double (2 hydroxy naphthalene base) fluorenes of 9,9- with ethylene carbonate
In, suitable polar aprotic solvent is added, promotes the solubility of alkali in organic solvent, since solid liquid phase transfers to use, promote
Into ethoxyl etherification, the reaction time is shortened, it is suppressed that the formation of by-product polymer, simplifies post-processing step, together
When the three wastes largely reduce, yield increases substantially, and obtains double [6- (2- hydroxy ethoxies) naphthalenes of 9,9- of high-purity high-bulk-density
Base] fluorenes.
The content of the invention
The present invention is directed to above-mentioned deficiency, and the hydroxyl hydroxyethylation of double (2 hydroxy naphthalene base) fluorenes of 9,9- is made with ethylene carbonate
In reaction, suitable polar aprotic solvent is added, shortens the reaction time, it is suppressed that the formation of by-product polymer, letter
Change post-processing step, while the three wastes are largely reduced, yield increases substantially.The present invention provides high-purity high-bulk-density
The preparation method of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of photoelectric material intermediate 9,9-.
The technical solution of the present invention
The synthesis technique and method of purification of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- of high-purity high-bulk-density, it is special
Sign is to comprise the following steps：
1）Double (2 hydroxy naphthalene base) fluorenes of 9,9- are added in reaction bulb, ethylene carbonate, alkali, reaction promoter and aromatic hydrocarbons are molten
Agent, be warming up to raw material it is complete it is molten after, 90oC-130oWhen C stirring reactions 5-6 is small.Sample double (the 2- hydroxyls of HPLC analysis raw materials 9,9-
Naphthyl) fluorenes content be less than 0.1%, stop reaction.
2）Step 1）After, water washing to neutrality.Cooling separates out solid, obtains the 9,9- of high-purity high-bulk-density
Double [6- (2- hydroxy ethoxies) naphthyl] fluorenes.
3）Step 2）Obtained solid is 80 ~ 100oWhen C dryings 6-12 is small, obtained product 9, double [6- (the 2- hydroxyl ethoxies of 9-
Base) naphthyl] fluorenes melting endothermic peak in 213-222oC。
4）Such as step 3）The purity of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of middle product 9,9-（HPLC）More than 99%.Product
The X- powder diffractions (XRPD) of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- are composed with such as pattern of attached drawing 3 and are with 2 θ values
7.7±0.20, 8.8±0.20, 12.5±0.20, 14.3±0.20, 15.5±0.20,17.7±0.20, 18.7±
0.20, 19.5±0.20, 20.4±0.20, 20.9±0.20, 21.2±0.20, 22.2±0.20, 22.7±0.20,
23.1±0.20, 24.8±0.20, 25.4±0.20, 25.9±0.20, 26.7±0.20Characteristic diffraction peak.Double [the 6- of 9,9-
(2- hydroxy ethoxies）Naphthyl] structure of fluorenes is。
Beneficial effects of the present invention：It is to use polar aprotic solvent to make the reaction time small from 10 for reaction promoter
When foreshorten to 6 it is small when or so, substantially increase production efficiency.The formation of by-product polymer is inhibited at the same time, is located after simplifying
Step is managed, while the three wastes are largely reduced, yield increases substantially.The present invention provides the photoelectric material of high-purity high-bulk-density
The preparation method of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of intermediate 9,9-.
Brief description of the drawings
Fig. 1 is the heat analysis DSC spectrums of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- prepared by the present invention.
Fig. 2 is the heat analysis TGA spectrums of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- prepared by the present invention.
Fig. 3 is X- powder diffractions (XRPD) spectrum of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- prepared by the present invention.
Embodiment
Method for detecting purity (HPLC)：Instrument：LC -15C （Shimadzu）；Column type：Kromasil100-5 C18 150×
4.6mm；Mobile phase：Acetonitrile/water；Flow velocity：1mL/min；Detection wavelength：260nm；Sample size：2ul；Pump pattern：Binary high pressure ladder
Degree.
Heat analysis method：Pyris1 thermal analyzers (Perkin Elemer companies) measure, DSC heated perimeters 50-
300oC, 10 oC/ minute；TGA heated perimeters are 25-300 oC, 10 oC/ minute.
X- powder diffractions (XRPD) are composed：X ' TRAX- x ray diffractometer xs (ARL Switzerland Co., Ltd) measure, copper target, continuous scanning
Pattern, 0.02 ° of scanning step (2 θ), 2.5 °/point of sweep speed.
Nuclear magnetic resoance spectrum：Bruker AM 500 MHz (Germany) nmr determinations (CD3SO CD3For solvent,
TMS is internal standard).
Embodiment 1
In 500mL reaction bulbs, double (2 hydroxy naphthalene base) the fluorenes 45.6g of 9,9- are added（0.1mol）, 200 mL of toluene, 20 g
DMAC, 1.0 g potassium carbonate and ethylene carbonate 22g（0.25mol）.In 110-115oWhen C back flow reactions 5-6 is small, HPLC points
The content for analysing double (2 hydroxy naphthalene base) fluorenes of 9,9- is less than 0.1%, stops reaction.Neutrality is washed with water to, separates organic phase cooling analysis
Go out solid, 80 ~ 100oAfter when C vacuum drying 12 is small, 9,9-, 45.8 g of double [6- (2- hydroxy ethoxies) naphthyl] fluorenes, yield are obtained
For 85.2%, high performance liquid chromatography（HPLC）Purity assay is 99.2%, and melting endothermic peak scope is in 213-222 oC（Attached drawing 1）,
Loss on drying is 0.10%, TGA heat analysis, 200 DEG C of weightlessness 0.2% (attached drawing 2) under the conditions of 120 degree；0.45g/ cubes of bulk density
Centimetre,1HNMR（CD3SOCD3）δ：3.76（T, 4H）, 4.05（T, 4H）, 4.87（S, 2H, add D2O disappears）, 7.01-7.10（D,
2H）,7.26-7.70（M, 16H）, 7.96（D, 2H）.X- powder diffractions (XRPD) are composed with such as pattern of attached drawing 3 and with 2 θ values
7.7±0.20, 8.8±0.20, 12.5±0.20, 14.3±0.20, 15.5±0.20,17.7±0.20, 18.7±
0.20, 19.5±0.20, 20.4±0.20, 20.9±0.20, 21.2±0.20, 22.2±0.20, 22.7±0.20,
23.1±0.20, 24.8±0.20, 25.4±0.20, 25.9±0.20, 26.7±0.20It is characterized diffraction maximum.
Embodiment 2 adds double (2 hydroxy naphthalene base) the fluorenes 45.6g of 9,9- in 500mL reaction bulbs（0.1mol）, toluene 200
ML, 20 g DMF, 1.0 g potassium carbonate and ethylene carbonate 22g（0.25mol）.In 110-115oC back flow reactions 5-6 is small
When, the content that HPLC analyzes double (2 hydroxy naphthalene base) fluorenes of 9,9- is less than 0.1%, stops reaction.Neutrality is washed with water to, has been separated
Machine mutually cools down precipitation solid, 80 ~ 100oAfter when C vacuum drying 12 is small, double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- are obtained
45.8 g, yield 82.7%, high performance liquid chromatography（HPLC）Purity assay is 99.1%, and melting endothermic peak scope is in 213-
222 oC, loss on drying is 0.2% under the conditions of 120 degree, 0.48g/ cubic centimetres of bulk density.
Embodiment 3 adds double (2 hydroxy naphthalene base) the fluorenes 45.6g of 9,9- in 500mL reaction bulbs（0.1mol）, toluene 200
ML, 20 g diglycol dimethyl ether, 1.0 g potassium carbonate and ethylene carbonate 22g（0.25mol）.In 110-115oC is returned
When stream reaction 5-6 is small, the content that HPLC analyzes double (2 hydroxy naphthalene base) fluorenes of 9,9- is less than 0.1%, stops reaction.It is washed with water to
Neutrality, separates organic phase cooling and separates out solid, 80 ~ 100oAfter when C vacuum drying 12 is small, double [6- (the 2- hydroxyl ethoxies of 9,9- are obtained
Base) naphthyl] 46.3 g of fluorenes, yield 86.0%, high performance liquid chromatography（HPLC）Purity assay is 99.3%, melts endothermic peak model
It is trapped among 213-222 oC, loss on drying is 0.2% under the conditions of 120 degree, 0.48g/ cubic centimetres of bulk density.
Embodiment 4 adds double (2 hydroxy naphthalene base) the fluorenes 45.6g of 9,9- in 500mL reaction bulbs（0.1mol）, toluene 200
ML, 20 g triethylene-glycol dimethyl ether, 1.0 g potassium carbonate and ethylene carbonate 22g（0.25mol）.In 110-115oC is returned
When stream reaction 5-6 is small, the content that HPLC analyzes double (2 hydroxy naphthalene base) fluorenes of 9,9- is less than 0.1%, stops reaction.It is washed with water to
Neutrality, separates organic phase cooling and separates out solid, 80 ~ 100oAfter when C vacuum drying 12 is small, double [6- (the 2- hydroxyl second of 9,9- are obtained
Epoxide) naphthyl] 45.7 g of fluorenes, yield 85.0%, high performance liquid chromatography（HPLC）Purity assay is 99.3%, melts endothermic peak
Scope is in 213-222 oC, loss on drying is 0.2% under the conditions of 120 degree, 0.5g/ cubic centimetres of bulk density.
Comparative example 1 adds double (2 hydroxy naphthalene base) the fluorenes 45.6g of 9,9- in 500mL four-hole boiling flasks（0.1mol）, toluene
200 mL, 1.0 g potassium carbonate and ethylene carbonate 22g（0.25mol）.In 110-115oWhen C back flow reactions 12-13 is small,
The content that HPLC analyzes double (2 hydroxy naphthalene base) fluorenes of 9,9- is less than 0.1%, stops reaction.Neutrality is washed with water to, separates organic phase
Cooling separates out solid, 80 ~ 100oAfter when C vacuum drying 12 is small, double [6- (2- hydroxy ethoxies) naphthyl] fluorenes 41.8 of 9,9- are obtained
G, yield 78.0%, high performance liquid chromatography（HPLC）Purity assay is 98.5%, and melting endothermic peak scope is in 213-222 oC,
0.35g/ cubic centimetres of bulk density.
Claims (9)
1. the present invention, using polar aprotic solvent as reaction promoter, 9,9- double (2 hydroxy naphthalene base) fluorenes and ethylene carbonate exist
Condensation prepares double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- of high-purity high-bulk-density under alkaline condition.
2. preparing the reaction promoter used in double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- as claimed in claim 1 includes N, N-
Dimethylacetylamide, n,N-Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, diglycol diformazan (or second)
Ether, triethylene-glycol diformazan (or second) ether, multicondensed ethylene glycol diformazan (or second) ether etc..
3. preparing the alkali used in double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- as claimed in claim 1 includes potassium carbonate, carbonic acid
Sodium, sodium acid carbonate, saleratus, triethylamine, pyridine etc..
4. solvent for use is aromatic hydrocarbons such as toluene, benzene, dimethylbenzene, ethylbenzene, diethylbenzene, different in reaction as claimed in claim 1
Propyl benzene etc..
5. if the reaction temperature in claim 1 is 90-130oC。
6. obtaining double [6- (2- hydroxy ethoxies) naphthyl] the fluorenes purity (HPLC analyses) of 9,9- as claimed in claim 1 is more than 99%,
Loss on drying<0.5% (120 DEG C, 30min).
7. as claimed in claim 1, bulk density is more than 0.4g/ cubic centimetres.
8. X- powder diffractions (XRPD) spectrum for obtaining double [6- (2- hydroxy ethoxies) naphthyl] fluorenes of 9,9- as claimed in claim 1 has
As attached drawing 3 pattern and with 2 θ values for 7.7 ± 0.20, 8.8±0.20, 12.5±0.20, 14.3±0.20, 15.5±
0.20,17.7±0.20, 18.7±0.20, 19.5±0.20, 20.4±0.20, 20.9±0.20, 21.2±0.20,
22.2±0.20, 22.7±0.20, 23.1±0.20, 24.8±0.20, 25.4±0.20, 25.9±0.20, 26.7±
0.20Characteristic diffraction peak.
9. as claimed in claim 1, the structure of 9,9- double [6- (2- hydroxy ethoxies) naphthyl] fluorenes isExplanation: C:Documents and Settings Administrator desktop structure .jpg。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711029609.1A CN108017521B (en) | 2017-10-30 | 2017-10-30 | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711029609.1A CN108017521B (en) | 2017-10-30 | 2017-10-30 | Preparation method of high-purity high-bulk-density 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene |
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| CN108017521B CN108017521B (en) | 2022-04-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018230394A1 (en) * | 2017-06-15 | 2018-12-20 | 田岡化学工業株式会社 | Method for producing alcohols having fluorene skeleton |
| CN114394887A (en) * | 2022-01-28 | 2022-04-26 | 江苏锐鸣材料科技有限公司 | Phenyloxyethanol compound and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155256A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
-
2017
- 2017-10-30 CN CN201711029609.1A patent/CN108017521B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155256A (en) * | 2007-12-26 | 2009-07-16 | Osaka Gas Co Ltd | Epoxy compound having fluorene skeleton |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018230394A1 (en) * | 2017-06-15 | 2018-12-20 | 田岡化学工業株式会社 | Method for producing alcohols having fluorene skeleton |
| CN114394887A (en) * | 2022-01-28 | 2022-04-26 | 江苏锐鸣材料科技有限公司 | Phenyloxyethanol compound and preparation method thereof |
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