CN108586205B - Preparation of 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal free from residual solvent in complex form - Google Patents
Preparation of 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal free from residual solvent in complex form Download PDFInfo
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- CN108586205B CN108586205B CN201810309148.1A CN201810309148A CN108586205B CN 108586205 B CN108586205 B CN 108586205B CN 201810309148 A CN201810309148 A CN 201810309148A CN 108586205 B CN108586205 B CN 108586205B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
The invention obtains the 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal without complex residual solvent through pulping and vacuum drying treatment of low-boiling point chlorine-containing solvent, thermal analysis and measurement of TGA spectrum shows that no complex residual solvent is generated, and melting endothermic peak on DSC spectrum is at 260-266 ℃. The characteristic 2 theta value of X-powder diffraction (XRPD) analysis is 8.3 +/-0.20(48),9.7±0.20(50),17.3±0.20(74),19.3±0.20(100),19.7±0.20(72),20.0±0.20(61),22.6±0.20(48),26.9±0.20(32). The crystal without the complexing residual solvent has the advantages that the solvent-free polycondensation reaction process is adopted to prepare materials such as polycarbonate, polyester, polyimide and the like, the release and dissipation of the residual and toxic and harmful solvents cannot be caused, the air environment is polluted, and meanwhile, the quality and the performance of the polymer material cannot be seriously influenced due to the release of the inclusion solvent in the reaction.
Description
Technical Field
The invention belongs to the technical field of photoelectric material intermediates, and particularly relates to a 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal free of a complexing residual solvent and a preparation method of a crystal form thereof.
Background
The 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene is an important intermediate of photoelectric materials, and materials such as polycarbonate, polyester, polyimide, epoxy resin, acrylic resin and the like which are derived and synthesized by the 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene have excellent properties such as high refractive index, high thermal stability, good transparency and the like, and have important application in the aspects of light guide devices, light emitting diode packaging materials, optical lenses, liquid crystal display brightness enhancement films, polarizing films, reflective films, electronic photoetching materials and the like. The preparation of these optical materials requires the highly inactive monomer 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene. However, 9-bis (6-hydroxynaphthalene-2-yl) fluorene is easily complexed with common organic solvents such as toluene, acetonitrile, methanol, ethyl acetate, etc., and the complexed organic solvents are included in the synthesis reaction and in the processes of crystallization and recrystallization after the reaction, and the solvent involved in the complexation is difficult to remove by methods such as vacuum drying, etc.
Chinese patent CN104230671 reports that a toluene solvate of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene obtained from toluene is treated with acetonitrile and ethyl acetate respectively and dried under vacuum to obtain the corresponding solvate. The 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal complexed with residual solvent has the disadvantages of releasing and dissipating residual toxic and harmful solvents, polluting air environment and seriously influencing the quality and performance of polymer materials due to the release of inclusion solvent in the reaction when materials such as polycarbonate, polyester, polyimide and the like are prepared by a solvent-free polycondensation reaction process. So far, no literature reports a crystallization method for preparing a solvent-free complex-encapsulated 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystal. On the other hand, the solvent involved in the complexation is difficult to remove by vacuum drying under reduced pressure above the boiling point of the solvent. Although the solvent involved in the complexation can be removed after the 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystal complexed with the residual solvent is heated to a temperature higher than the melting point and melted, the melting point is high, the product is liable to be colored when melted at high temperature, and it is difficult to industrially implement. The structural formula of the 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene is as follows:
disclosure of Invention
The invention aims at the problems and researches and develops a crystallization method for preparing the solvent-free complex inclusion 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal. Aims to provide a high-purity 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal without solvent complexing inclusion and a preparation method thereof, which has low cost and is easy to implement industrially.
The technical solution of the invention is as follows:
the inventor researches and discovers that the solvate can be obtained by recrystallizing aromatic hydrocarbons, aliphatic hydrocarbons, ethers, ketones, esters, nitriles and other solvents and then drying in vacuum. However, the inventor researches and discovers that the recrystallization treatment by using a low-boiling point chlorine-containing solvent has different effects, and the 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal without solvent inclusion and complexation can be obtained after vacuum drying under the same conditions. The process for preparing the solvent-free inclusion complex 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal comprises the following steps:
1) the crude product was synthesized by a conventional method. Adding 9-fluorenone, 2-naphthol, cocatalyst 3-mercaptopropionic acid and toluene into a reaction bottle, stirring until the 9-fluorenone and the 2-naphthol are dissolved, slowly dropwise adding 98% sulfuric acid, and stirring for reacting for 4-8 hours at 50-60 ℃ after dropwise adding; after the reaction is finished, adding 10% sodium hydroxide for neutralization to neutrality, adding water for washing at 80 ℃, separating an organic layer, evaporating the solvent under reduced pressure, adding methanol, and stirring to separate out a solid which is a crude product;
2) and (3) recrystallizing the crude product obtained in the step (1) by using a low-boiling point chlorine-containing solvent, and cooling to 0 ℃ at a speed of 0.3-1.0 ℃/min while stirring for crystallization.
3) And (3) drying the crystal obtained in the step (2) in vacuum for 5-10 hours at the temperature of 100 ℃/1.33 kPa.
The invention has the beneficial effects that:
the invention has unexpected beneficial effect on the crude product obtained by recrystallization treatment reaction with low-boiling point chlorine-containing solvent, obtains the high-purity (not less than 98%) 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal without solvent inclusion and complexation, and the TGA spectrum (shown in figure 2) determined by thermal analysis shows that no complexing residual solvent exists, and the DSC spectrum (shown in figure 3) has a melting endothermic peak at 260-266 ℃. The preparation method is easy to implement industrially. The X-ray powder diffraction (XRPD) spectrum (see fig. 1) shows that its crystalline form is completely different from that of the complex with solvent. Chinese patent CN104230671 is obtained by respectively recrystallizing with acetonitrile and ethyl acetate and vacuum drying. In the comparative example, even if the vacuum drying temperature is raised to 150 ℃ and the drying time is prolonged to 20 hours after recrystallization treatment with an aromatic hydrocarbon solvent such as toluene, the TGA spectrum (see figure 5) still shows that the complexing residual toluene is about 4%, the main melting endothermic peak on the DSC spectrum (see figure 6) is 231-235 ℃ which is 30 ℃ lower than that of the product without solvent inclusion complexing, the purity is 98.2%, and the 2 theta value (see figure 4) of the X-ray powder diffraction (XRPD) spectrum shape and characteristics is different from that of the crystal form without solvent complexing. Therefore, the solvent-free inclusion complex high-purity (98 percent or more) 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal and the preparation method thereof have important values for synthesizing high-quality optical materials such as polycarbonate, polyester, polyimide and the like.
Drawings
FIG. 1 is an X-powder diffraction (XRPD) spectrum of a solvent-free inclusion complex-free 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystal according to the present invention.
FIG. 2 is a TGA spectrum of a crystal of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene complexed without solvent inclusion according to the present invention.
FIG. 3 is a DSC spectrum of the crystal of the present invention without solvent inclusion complex of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene.
FIG. 4 is an X-powder diffraction (XRPD) spectrum of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystals recrystallized from toluene of comparative example.
FIG. 5 is a TGA analysis spectrum of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystals recrystallized from toluene of comparative example.
FIG. 6 is a DSC analysis spectrum of a crystal of 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene recrystallized from toluene of comparative example.
Detailed Description
Purity determination method (HPLC):
the instrument comprises the following steps: LC-15C (Shimadzu); column type: kromasil 100-5C18150X 4.6 mm; mobile phase: methanol: 70:30 parts of water; flow rate: 1.0 ml/min; detection wavelength: 285 nm; sample introduction amount: 2 ul; pump mode: a binary high pressure gradient.
Crystal form determination method (XRPD analysis):
the X-ray powder diffraction spectrum was measured by an X' TRA X-ray diffractometer (ARL, Switzerland), copper and palladium, in a continuous scanning mode, with a scanning step of 0.02 DEG (2 theta) and a scanning speed of 2.5 DEG/min.
Crystal thermal analysis method:
pyris1 thermal analyzer (Perkin Elemer company) with DSC heating range of 50-300 deg.C, 10 deg.C/min, TGA heating range of 25-500 deg.C, 20 deg.C/min.
Example 1
9-fluorenone (18g,0.1mol), 2-naphthol (33.1g,0.23mol), 3-mercaptopropionic acid (1.0g), and 200mL of toluene were charged into a reaction flask, and after stirring and dissolving, 20.2g (0.2mol) of 98% sulfuric acid was slowly dropped. Stirring and reacting for 4-8 hours at 50-60 ℃. HPLC analysis confirmed that the reaction was stopped when the 9-fluorenone content was 0.1% or less. Adding 10% sodium hydroxideNeutralized to neutral, 3 × 100mL water washed at 80 ℃. The organic layer was separated, the solvent was distilled off under reduced pressure, 100mL of methanol was added, and the mixture was stirred to precipitate crystals. Recrystallizing with 1-chloropropane, and cooling to 0 ℃ at the speed of 0.3-1.0 ℃/min while stirring for crystallization. The crystals were filtered and dried under vacuum at 100 deg.C/1.33 kPa for 8 hours to give 33.8 g of crystals in 75.0% yield and 99.3% purity by HPLC analysis.1HNMR (500MHz, CDCl3) delta: 7.00-7.12(m,4H),7.37-7.41(m,2H),7.51-7.57(m,14H),7.82-7.97(d,2H). TGA spectrum (see FIG. 2) shows no complexing residual solvent, and melting endotherm at 260-266 ℃ on DSC spectrum (see FIG. 3). X-powder diffraction analysis (see FIG. 1)2 θ (relative intensity%): 8.3. + -. 0.20(48), 9.7. + -. 0.20(50), 17.3. + -. 0.20(74), 19.3. + -. 0.20(100), 19.7. + -. 0.20(72), 20.0. + -. 0.20(61), 22.6. + -. 0.20(48), 26.9. + -. 0.20 (32).
Example 2
Synthesizing by the same steps to obtain a crude product, then recrystallizing by using 1, 2-dichloroethane, and cooling to 0 ℃ for crystallization at a speed of 0.3-1.0 ℃/min while stirring. The crystals were filtered and dried under vacuum at 100 deg.C/1.33 kPa for 8 hours to give 36.5 g of crystals in 81.0% yield and 99.5% purity by HPLC analysis. The X-ray powder diffraction spectrum shows the same crystal form as example 1.
Example 3
And (3) synthesizing by the same steps to obtain a crude product, then recrystallizing by using chloroform, and cooling to 0 ℃ for crystallization at a speed of 0.3-1.0 ℃/min under stirring. The crystals were filtered and dried under vacuum at 100 deg.C/1.33 kPa for 8 hours to give 33.5 g of crystals in 74.5% yield and 99.2% purity by HPLC analysis. The X-ray powder diffraction spectrum shows the same crystal form as example 1.
Comparative example
And synthesizing by the same steps to obtain a crude product, then recrystallizing by using toluene, and cooling to 0 ℃ for crystallization at a speed of 0.3-1.0 ℃/min while stirring. The crystals were filtered and dried under vacuum at 100 deg.C/1.33 kPa for 8 hours. The residual solvent content was analyzed to be 5%. The vacuum drying is continued for 12 hours by increasing the temperature to 150 ℃/1.33 kPa. No significant reduction in residual solvent content was analyzed (fig. 4). 36.6 g of crystals are obtained in 81.5% yield and 98.2% purity by HPLC analysis. The TGA spectrum (see FIG. 5) shows that about 4.3% of the complexed residual toluene still remains, and the DSC spectrum (see FIG. 6) has a main melting endothermic peak 231-. Characteristic 2 theta values (see FIG. 4) for X-ray powder diffraction (XRPD) analysis were 4.0. + -. 0.20(87), 8.2. + -. 0.20(84), 10.8. + -. 0.20(59), 12.3. + -. 0.20(68), 14.2. + -. 0.20 (98), 16.6. + -. 0.20(96), 19.0. + -. 0.20 (72).
Claims (3)
1. 9, 9-bis (6-hydroxynaphthalene-2-yl) fluorene crystal without complexing residual solvent has a melting endothermic peak at 260-266 ℃.
2. The 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystal free of residual solvent complex according to claim 1, which has the morphology of X-powder diffraction spectrum shown in fig. 1.
3. A process for producing a 9, 9-bis (6-hydroxynaphthalen-2-yl) fluorene crystal free from residual solvent by complexation as claimed in claim 1 or 2, comprising the steps of: recrystallizing the crude product obtained by the reaction with a low-boiling point chlorine-containing solvent, and then drying the crude product for 5 to 10 hours in vacuum at 100 ℃; the low-boiling point chlorine-containing solvent is dichloromethane, chloroform, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chlorobutane or 1-chlorobutane.
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