CN112189003A - Crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl - Google Patents
Crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl Download PDFInfo
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- CN112189003A CN112189003A CN201980034683.3A CN201980034683A CN112189003A CN 112189003 A CN112189003 A CN 112189003A CN 201980034683 A CN201980034683 A CN 201980034683A CN 112189003 A CN112189003 A CN 112189003A
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
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Abstract
The present invention addresses the problem of providing a novel crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl, which is suitable as a resin raw material having excellent optical properties. As a solution, it was found that a crystalline 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl having an endothermic peak top temperature in a specific range obtained by differential scanning calorimetry and a loose bulk density in a specific range, represented by the following chemical formula, can be obtained by crystallization using a specific solvent. [ chemical formula1]
Description
Technical Field
The present invention relates to a novel crystal of a dicarboxylic acid compound and a method for producing the same. Specifically, the present invention relates to a crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl having an endothermic peak top temperature in a specific range obtained by differential scanning calorimetry and a loose bulk density in a specific range.
Background
In recent years, polyester resins and polyester carbonate resins containing a dicarboxylic acid component having a binaphthyl skeleton as a polymerization component have excellent chemical properties such as high refractive index and low birefringence, and have high heat resistance, and thus are expected to be used as materials for optical members such as optical disks, transparent conductive substrates, and optical filters. Among them, a resin produced using 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl (hereinafter, referred to as "compound a") having a chemical structure represented by the following chemical formula as a polymerization component has attracted particular attention because of its excellent optical properties (for example, patent documents 1 to 4 and the like).
[ chemical formula 1]
As a method for producing the compound a represented by the above formula, a method is known in which 1,1 '-binaphthyl-2, 2' -diol is reacted with a halogenated acetate such as ethyl chloroacetate, and the obtained diester is hydrolyzed, as represented by the following reaction formula (for example, patent document 5). However, since the compound a obtained by this reaction is often used by directly converting an unrefined crude product into an acid chloride by thionyl chloride, oxalyl chloride, or the like, studies and reports on a purification method have not been completed.
[ chemical formula 2]
Further, the present inventors have found that crystals having different characteristics are present in the dicarboxylic acid compound during the repeated production of the compound a.
Documents of the prior art
Non-patent document
Patent document 1: japanese patent laid-open No. 2001 and 072872
Patent document 2: japanese patent laid-open publication No. 2018-002893
Patent document 3: japanese patent laid-open publication No. 2018-002894
Patent document 4: japanese patent laid-open publication No. 2018-002895
Patent document 5: japanese patent laid-open No. 2008-024650
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel crystal of compound a suitable as a resin raw material having excellent optical characteristics.
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that a crystal of compound a having an endothermic peak top temperature in a specific range obtained by differential scanning calorimetry and a loose bulk density in a specific range can be obtained by crystallization using a specific solvent, and have completed the present invention.
The present invention is as follows.
1. A crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl characterized by having an endothermic peak top temperature of 215 to 220 ℃ as measured by differential scanning calorimetry and a loose bulk density of 0.3 to 0.6g/cm3The range of (1).
2. The crystalline 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl compound according to 1, wherein a 30 wt% solution of the crystalline in tetrahydrofuran has a Hazen color APHA of 100 or less.
3. A method for producing a crystal according to 1.or 2, characterized in that the crystal is crystallized from any one of the following solvents (1) to (5):
(1) one or more selected from chain ketone solvents having a total carbon number of 5 to 8,
(2) one or more cyclic ketone solvents having 5 to 8 total carbon atoms,
(3) at least one selected from cyclic ether solvents having 4 to 8 total carbon atoms,
(4) one or more cyclic ester solvents having 4 to 8 total carbon atoms,
(5) more than one kind of chain ketone solvent with 3-8 total carbon atoms and water.
4. The production method according to claim 3, characterized in that the crystallization is carried out by any one of the following solvents (1 ') to (5'):
(1') methyl isobutyl ketone or 2-octanone,
(2') a cyclohexanone (a) and (b),
(3') tetrahydrofuran or 1, 4-dioxane,
(4') gamma-butyrolactone or gamma-valerolactone,
(5') a mixed solvent of acetone and water or a mixed solvent of methyl ethyl ketone and water.
The present invention can provide a crystal of compound a having an endothermic peak top temperature in a specific range obtained by differential scanning calorimetry and a loose bulk density in a specific range.
The crystal of the present invention has a high endothermic peak top temperature obtained by differential scanning calorimetry and a high loose bulk density, and therefore, the production, use, transportation, etc. of the compound can be effectively carried out. Furthermore, when an optical resin is produced using a crystal of the compound as a raw material, dust scattering can be suppressed, adhesion to production facilities and clogging can be prevented, and in addition, the capacity of a reaction vessel used as a reaction raw material can be reduced, and improvement in productivity can be expected. Further, the capacity of the container during transportation can be reduced, the transportation cost can be reduced, and excellent effects can be obtained in terms of operability.
Further, the crystal of the present invention can be obtained by crystallization operation, and thus has excellent characteristics of high purity and low coloring.
That is, the crystal and the method for producing the same according to the present invention are very useful for industrial use of resin materials and the like.
Drawings
Fig. 1 is a graph showing differential scanning calorimetry analysis data of the crystalline solid obtained in example 1.
Fig. 2 is a graph showing differential scanning calorimetry analysis data of the crystalline body obtained in example 2.
Fig. 3 is a graph showing differential scanning calorimetry analysis data of the crystalline solid obtained in example 3.
Fig. 4 is a graph showing differential scanning calorimetry analysis data of the solid obtained in comparative example 1.
Fig. 5 is a graph showing differential scanning calorimetry analysis data of the solid obtained in comparative example 2.
Detailed Description
The present invention will be described in detail below.
The compound a of the present invention is a compound represented by the following chemical formula.
[ chemical formula 3]
< synthetic method >
The method for synthesizing the compound a of the present invention is not particularly limited, and examples thereof include a known production method in which a diester is obtained by reacting 1,1 '-binaphthyl-2, 2' -diol with a halogenated acetate such as ethyl chloroacetate, and the diester is then hydrolyzed.
[ chemical formula 4]
< about the crystallization Process >
The production method of the present invention is characterized in that crystallization is performed by any one of the following solvents (1) to (5): (1) more than one selected from chain ketone solvents with 5-8 total carbon atoms, (2) more than one selected from cyclic ketone solvents with 5-8 total carbon atoms, (3) more than one selected from cyclic ether solvents with 4-8 total carbon atoms, (4) more than one selected from cyclic ester solvents with 4-8 total carbon atoms, and (5) more than one selected from chain ketone solvents with 3-8 total carbon atoms and water.
Examples of the chain ketone solvent (1) having a total carbon number of 5 to 8 that can be used herein include diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and 2-octanone, and among them, methyl isobutyl ketone, methyl amyl ketone, and 2-octanone having low solubility in water are preferable. The cyclic ketone solvent (2) having a total carbon number of 5 to 8 that can be used includes cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and the like, and among them, cyclopentanone and cyclohexanone are preferable. Examples of the cyclic ether solvent (3) having 4 to 8 total carbon atoms include oxetane, tetrahydrofuran, tetrahydropyran, and 1, 4-dioxane, and tetrahydrofuran and 1, 4-dioxane are preferable. Examples of the cyclic ester solvent (4) having 4 to 8 total carbon atoms include γ -butyrolactone, γ -valerolactone, σ -valerolactone and caprolactone, and among them, γ -butyrolactone and γ -valerolactone are preferable. Examples of the chain ketone solvent (5) used as a mixed solvent with water include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and 2-octanone, and among them, acetone and methyl ethyl ketone having high solubility in water are preferable. The water to be used is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, natural water, and the like can be suitably used.
The compound a used in the crystallization step of the present invention includes a crude crystal obtained by treating a reaction solution containing the compound a, a crystal obtained by recrystallizing the crude crystal, a residual liquid obtained by distilling off a solvent from a solution containing the compound a, and the like. Or may be amorphous. Although 2 kinds of enantiomers exist in the compound a itself, a racemate is preferable as the compound a used in the crystallization step of the present invention, and a racemate is also preferable as the crystal obtained.
When the chain ketone solvent (1) such as methyl isobutyl ketone or methyl amyl ketone, which is used without being prepared as a mixed solvent with water, is used, the amount of the solvent for dissolving the compound a is preferably 250 to 1000 parts by weight, more preferably 300 to 800 parts by weight, and still more preferably 400 to 600 parts by weight, based on 100 parts by weight of the compound a contained in the crystals and the solution used. When the temperature is raised to dissolve the crystals completely, the pressure may be either normal pressure or increased, and when the temperature is 450 parts by weight or less, the pressure is preferably increased. The solution obtained by dissolving the compound a in the ketone solvent may be directly cooled and crystallized, or may be cooled and crystallized at the same time as or after distilling off the ketone solvent from the solution by distillation. When the compound a is dissolved in the solvent using 500 parts by weight or more of the chain ketone solvent per 100 parts by weight of the compound a, the ketone solvent is preferably distilled off in order to improve the yield. The amount of the chain ketone solvent in the residue after the solvent distillation is preferably adjusted to 150 to 450 parts by weight, more preferably 200 to 400 parts by weight, and still more preferably 250 to 300 parts by weight, based on 100 parts by weight of the crystals used. The temperature for precipitating crystals is preferably 90 to 130 ℃, more preferably 95 to 105 ℃. The time taken for distilling off the solvent is preferably 2 to 15 hours, more preferably 4 to 10 hours, and still more preferably 6 to 8 hours. The ketone solution of compound a can be obtained by adding the above-mentioned chain ketone solvent to an aqueous solution in which the alkali metal salt of compound a is dissolved, and then adding an acid thereto. Then, the aqueous layer is separated, and the water layer is separated and removed by adding water to the obtained solvent layer and stirring, and then the same operation as described above is performed to precipitate crystals of the compound a.
When any one of the cyclic ketone solvent (2), the cyclic ether solvent (3) and the cyclic ester solvent (4) is used, the amount of the solvent for dissolving the compound a is preferably 50 to 600 parts by weight, more preferably 50 to 400 parts by weight, and further preferably 100 to 200 parts by weight, based on 100 parts by weight of the compound a contained in the crystals and the solution used. When the temperature is elevated to completely dissolve the crystals, the reaction may be carried out under normal pressure or under pressure. The compound a may be directly cooled and crystallized in a solution obtained by dissolving the compound a in any one of the cyclic ketone solvent (2), the cyclic ether solvent (3) and the cyclic ester solvent (4), or may be cooled and crystallized simultaneously with or after distilling off the solvent from the solution by distillation. When a cyclic ketone solvent is used as the temperature for precipitating crystals, the temperature is preferably 90 to 110 ℃, and more preferably 100 ℃. When a cyclic ether solvent is used, the temperature is preferably 55 to 75 ℃ and more preferably 60 to 70 ℃. When a cyclic ester solvent is used, the temperature is preferably 90 to 130 ℃ and more preferably 115 to 125 ℃.
When the mixed solvent (5) of the chain ketone solvent and water is used, the concentration of the chain ketone solvent in the mixed solvent in which the compound a is dissolved is preferably 95 to 65% by weight, more preferably 90 to 70% by weight, and still more preferably 85 to 75% by weight. The amount of the mixed solvent used is preferably 100 to 350 parts by weight, more preferably 150 to 250 parts by weight, based on 100 parts by weight of the compound a. When the compound a is added to the mixed solvent (5) of the chain ketone solvent and water and heated, a solution in which the compound a is dissolved in the mixed solvent (5) of the chain ketone solvent and water can be obtained, but since direct cooling may not cause crystallization or may result in a low yield depending on the amount of the solvent and the amount of water, it is preferable to precipitate crystals by adding water to a solution in which the compound a is dissolved in the chain ketone solvent having a total carbon number in the range of 3 to 8, or to precipitate crystals by adding water and then cooling. The weight ratio of the chain ketone solvent to water in the crystallization liquid after addition of water is preferably 150 to 400 parts by weight, more preferably 230 to 300 parts by weight, based on 100 parts by weight of the chain ketone solvent. The crystallization temperature when water is added to the mixed solvent is preferably 55 to 65 ℃, more preferably about 60 ℃. The time for adding water is preferably 1 to 5 hours, more preferably 1.5 to 2.5 hours, and still more preferably about 2 hours.
In the crystallization operation using any of the solvents (1) to (5), the cooling rate during crystallization and after crystallization is preferably 5 to 15 ℃ per hour, more preferably 7 to 12 ℃. In addition, when the crystal is precipitated, a seed crystal may not be used, but a seed crystal may be preferably used, and the crystal precipitated without the seed crystal may be used as the seed crystal. The final cooling temperature is preferably 20 to 60 ℃, and more preferably 25 to 35 ℃. After cooling to the above temperature, the precipitated crystals were separated by filtration.
< drying Process >
The crystals obtained by crystallization are dried to remove the solvent used in crystallization. The crystallization can be carried out under normal pressure or under reduced pressure when the crystals obtained by crystallization are dried, but in the case of industrial practice, the solvent used in crystallization can be removed more efficiently, and therefore, the crystallization is suitably carried out under reduced pressure. The reaction can be carried out preferably under reduced pressure of 60 to 120 ℃ and more preferably under reduced pressure of 70 to 110 ℃.
< crystals of the present invention >
The crystal of the present invention is characterized in that the endothermic peak top temperature obtained by differential scanning calorimetry is in the range of 215 to 220 ℃ and the loose bulk density is 0.3 to 0.6g/cm3The range of (1).
The loose bulk density of the present invention is generally obtained by uniformly charging particles to be measured into a container having a predetermined volume so as not to form a cavity and not to apply an external force such as vibration to the container, measuring the weight at that time, and obtaining a value obtained by dividing the weight by the volume of the container, and is calculated from the measurement result by the method described below using, for example, a Multi Tester (MT-1001, manufactured by SEISHIN corporation, ltd.) or the like. The loose bulk density of the crystal is 0.3-0.6 g/cm3Larger values are preferred within the range of (1). The lower limit value within this numerical range is preferably 0.33g/cm3Above, more preferably 0.4g/cm3The above. The upper limit of this numerical range is preferably closer to 0.6g/cm3The value of (b) may be 0.55g/cm3Below or 0.5g/cm3About the following.
The crystals shown in the comparative examples described later were crystals having endothermic peak tops of 210 ℃, 214 ℃ and 215 ℃ obtained by differential scanning calorimetry, but had a loose bulk density of 0.12g/cm3～0.23g/cm3Therefore, it is considered that the crystals of the present invention have a greater improvement in loose bulk density than those of the comparative examples. That is, the crystals of the present invention can suppress dust and prevent adhesion and clogging to production facilities, and can reduce the capacity of a reaction vessel used as a reaction raw material and a vessel used for transportation, thereby improving productivity, reducing transportation cost, and the like, and can exhibit excellent effects in terms of handling.
The crystal of the present invention has an excellent characteristic of low coloration, and specifically, a 30 wt% solution obtained by dissolving the crystal in tetrahydrofuran (purity of 97% or more) preferably has a Hazen color (APHA) of 100 or less. Among these, the Hazen color (APHA) is more preferably 80 or less, still more preferably 60 or less, and most preferably 30 or less. In order to obtain the low-colored crystal of the present invention, the crystallization step is preferably performed in an inert gas atmosphere such as nitrogen, and the drying step is preferably performed in an inert gas atmosphere such as nitrogen or under reduced pressure.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
The analytical method is as follows.
< analytical method >
1. Differential Scanning Calorimetry (DSC)
The crystals were precisely weighed into an aluminum pan, and measured using a differential scanning calorimetry apparatus (DSC-60, manufactured by Shimadzu corporation) under the following operating conditions with alumina as a control.
(operating conditions)
Temperature rise rate: 10 ℃/min
Measurement temperature range: 30-260 deg.C
And (3) measuring atmosphere: open, nitrogen 50mL/min
Sample amount: 3 mg. + -. 1mg
2. Bulk density of bulk
Using a multifunctional powder physical Property Tester, a Multi Tester (MT-1001 model, Seishin corporation) was used to stably charge crystals into a volume of 20cm through a sieve without generating an air gap3The loose bulk density of the measurement cell (2) is calculated by measuring the crystal weight a (g) in the measurement cell after the measurement cell is filled with the crystals and using the following equation.
[ calculation formula ]
Bulk density of bulk (g/cm)3) Weight of crystal a (g)/20 cm3
3. Powder X-ray diffraction (XRD)
0.1g of the crystal was filled in a sample-filled area of a glass test plate, and measured under the following conditions using a powder X-ray diffraction apparatus (manufactured by Rigaku corporation: SmartLab).
4. Hue (APHA)
The crystals were dissolved in tetrahydrofuran (Fuji photograph film and Wako pure chemical industries, purity: 97% or more) to obtain a 30 wt% solution, and the dissolved color of the 30 wt% solution was measured after "calibration" by the following measuring instrument was performed with tetrahydrofuran.
The measuring instrument: TZ 6000, manufactured by Nippon Denshoku industries Ltd
< example 1 >
Crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl (compound A)
(1 thereof)
52g of 1,1 '-binaphthyl-2, 2' -diol (hereinafter referred to as "compound b"), 156g of N-methylpyrrolidone, 58g of potassium carbonate, and 5.2g of potassium iodide were charged into a four-necked flask, and the flask was heated to 70 ℃ and stirred at the same temperature for 1 hour. While maintaining the temperature of the reaction solution at 65 to 70 ℃, 62g of ethyl chloroacetate was added dropwise. After stirring for 4 hours, 156g of water and 30g of potassium hydroxide were added, and the mixture was stirred at 85 to 90 ℃ for 13 hours. Then, 130g of water and 156g of methyl isobutyl ketone (hereinafter, referred to as "MIBK") were added, and the mixture was stirred at 80 to 85 ℃ for 15 minutes, after which an aqueous layer was extracted and transferred to another four-neck reaction flask. To the water layer were added MIBK416g and 416g of water, and 100g of concentrated hydrochloric acid was added dropwise while maintaining the temperature at 80 to 85 ℃, followed by stirring at the same temperature for 30 minutes. Then, the mixture was allowed to stand to remove the aqueous layer, and water was added to the resulting oil layer and stirred, followed by allowing to stand to remove the aqueous layer. From the resulting oil layer, water and MIBK252g were distilled off over 4 hours by atmospheric distillation with stirring. After 1 hour from the start of the distillation, crystals were precipitated without adding a seed crystal. Thereafter, the reaction mixture was cooled to 25 ℃ at a cooling rate of 10 ℃ per hour, and the precipitated crystals were filtered and dried to obtain 60.7g (yield: 82%) of compound A as powdery crystals.
Purity of 98.7% by high performance liquid chromatography, endothermic peak top temperature of 217 ℃ by differential scanning calorimetry, and loose bulk density of 0.34g/cm3The hue (APHA) was 50.
A graph showing differential scanning calorimetry data is shown in FIG. 1 (sample amount: 2.311 mg).
< example 2 >
Crystal of Compound A (2 thereof)
Compound b1213g, acetonitrile 3638g, potassium carbonate 1346g, and potassium iodide 121g were charged in a four-necked flask, and the mixture was heated to 70 ℃ and stirred at the same temperature for 1 hour. After a mixed solution of 1460g of ethyl chloroacetate and 13g of N-methylpyrrolidone was prepared, the mixed solution was added dropwise while maintaining the temperature of the reaction solution at 70 to 80 ℃. After stirring for 6 hours, 3032g of water was added, and the temperature was raised to 70 ℃ to remove the water layer. Next, 3392g of a 35% potassium hydroxide aqueous solution was added dropwise while keeping the temperature of the reaction solution at 70 to 80 ℃. After 2 hours, the reaction mixture was slowly cooled and filtered at 25 ℃ to obtain 2180g of potassium salt crystals of compound A.
Next, a crystallization step was performed in a nitrogen atmosphere. Using 2051g (solvent-attached portion: about 16 wt%) of the obtained potassium salt crystals, 3430g of water and MIBK9702g were put into a four-necked flask, and the mixture was dissolved by heating to 80 ℃. 1207g of concentrated hydrochloric acid was added dropwise while keeping the temperature at 80 to 85 ℃ and stirred at the same temperature for 30 minutes. Then, the aqueous layer was extracted, and water was added thereto to carry out water washing. Subsequently, water and MIBK4713g were distilled off from the resulting oil layer by distillation at normal pressure over 8 hours. At a point of time 2 hours after the start of distillation, 1g of the crystal obtained in example 1 was added as a seed crystal, and crystallization was performed. The crystallization liquid was cooled to 25 ℃ at a cooling rate of 10 ℃ per hour, filtered, and then dried under reduced pressure to obtain 1392g of crystals of Compound A (yield: 86.8%).
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 217 ℃ by differential scanning calorimetry, and loose bulk density of 0.45g/cm3The hue (APHA) was 30. In addition, XRD is characterized by a2 theta (deg) of 8.1, 9.2, 14.8, 16.2, 17.5, 18.2, 18.5, 22.7, 23.4, 24.4, 26.9, 27.5, 31.5, 36.3, 39.2.
A graph showing differential scanning calorimetry data is shown in FIG. 2 (sample amount: 2.952 mg).
< example 3 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A607g and 1220g of 80% aqueous acetone solution were placed in a four-necked flask, and the temperature was raised to 50 ℃ to dissolve the compound. 1100g of water was added while maintaining the internal temperature at 55 to 60 ℃. Thereafter, 1g of the crystal obtained in example 1 was added as a seed crystal, and 1100g of water was added over 2 hours while maintaining the temperature at 55 to 60 ℃ to conduct crystallization. The crystallization liquid was cooled to 25 ℃ at a cooling rate of 10 ℃ per hour, filtered, and then dried under reduced pressure to obtain 552g of the crystal of the present invention (purification yield: 90.9%).
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 218 ℃ by differential scanning calorimetry, and loose bulk density of 0.46g/cm3The hue (APHA) was 20. In addition, XRD is characterized by a2 theta (deg) of 8.1, 9.2, 14.8, 16.2, 18.5, 23.4, 24.4, 26.9, 27.5, 31.5, 36.3, 39.2.
A graph showing differential scanning calorimetry data is shown in FIG. 3 (sample amount: 1.988 mg).
< example 4 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A20g and 120g of 2-octanone were placed in a four-necked flask, the temperature was raised to 145 ℃ to dissolve the compound, and then the mixture was cooled at a cooling rate of 10 ℃ per hour to confirm the precipitation of crystals at 127 ℃. Then, the crystallization liquid was cooled to 25 ℃ and filtered, followed by drying under reduced pressure, whereby 18.5g of the crystal of the present invention was obtained (purification yield: 92.5%).
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.35g/cm3The hue (APHA) was 20. In addition, XRD is characterized by 2 θ (deg) of 8.1, 9.2, 14.8, 16.1, 18.2, 22.5, 23.4, 24.3, 26.8, 36.3.
< example 5 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A20g and 38.7g of a 90% methyl ethyl ketone aqueous solution were placed in a four-necked flask, heated to 72 ℃ to dissolve the compound, and then cooled at a cooling rate of 10 ℃ per hour to confirm the deposition of crystals at 55 ℃. Then, the crystallization liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 6.5g of the crystal of the present invention.
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 216 ℃ by differential scanning calorimetry, and loose bulk density of 0.32g/cm3The hue (APHA) was 10. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.6, 16.2, 18.2, 22.5, 23.3, 24.3, 26.8, 36.3.
< example 6 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. 20.1g of the compound A and 20.2g of cyclohexanone were charged into a four-necked flask, and the mixture was heated to 146 ℃ to dissolve the compound A, and then cooled at a cooling rate of 10 ℃ per hour to confirm the deposition of crystals at 103 ℃. Then, the crystallized liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 13.7g of crystals of the present invention.
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.34g/cm3The hue (APHA) was 40. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.8, 16.2, 18.2, 23.4, 24.3, 26.8, 36.3.
< example 7 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A15g and 15.9g of tetrahydrofuran were charged into a four-necked flask, and the mixture was heated to 65 ℃ to dissolve it, and then cooled at a cooling rate of 10 ℃ per hour, and precipitation of crystals was confirmed at 59 ℃. Then, the crystallization liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 7.5g of the crystal of the present invention.
Purity of 99.8% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.43g/cm3The hue (APHA) was 60. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.8, 16.2, 18.2, 18.4, 22.5, 23.4, 24.3, 26.8, 36.3.
< example 8 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. 15.1g of the compound A and 17.5g of 1, 4-dioxane were charged into a four-necked flask, and the mixture was heated to 101 ℃ to dissolve the compound, and then cooled at a cooling rate of 10 ℃ per hour, and precipitation of crystals was confirmed at 70 ℃. Then, the crystallization liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 8.0g of the crystal of the present invention.
Purity of 99.4% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.41g/cm3The hue (APHA) was 80. In addition, XRD is characterized by 2 θ (deg) of 8.1, 14.6, 16.1, 18.2, 22.5, 23.4, 24.4, 26.8, 36.3.
< example 9 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A15g and 10g of gamma-butyrolactone were placed in a four-necked flask, the temperature was raised to 140 ℃ to dissolve the compound, and then the flask was cooled at a cooling rate of 10 ℃ per hour to confirm the precipitation of crystals at 103 ℃. Then, the crystallized liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 13.1g of crystals of the present invention.
Obtained by high performance liquid chromatographyHas a purity of 99.8%, an endothermic peak top temperature of 215 ℃ obtained by differential scanning calorimetry, and a loose bulk density of 0.33g/cm3The hue (APHA) was 130. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.7, 16.1, 18.2, 22.5, 23.3, 24.3, 26.8, 36.3.
< example 10 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A20g and gamma-valerolactone (20 g) were placed in a four-necked flask, heated to 135 ℃ and dissolved, and then cooled at a cooling rate of 10 ℃ per hour, and precipitation of crystals was confirmed at 123 ℃. Then, the crystallized liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 16.7g of the crystal of the present invention.
Purity of 99.7% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.44g/cm3. In addition, XRD is characterized by 2 θ (deg) of 8.0, 14.6, 16.1, 18.1, 23.3, 24.3, 26.9, 36.2.
< comparative example 1 >
Compound b4.0g, potassium carbonate 34.8g, bromoacetic acid 20.1g, and methanol 118mL were charged into a four-necked flask, and reacted under reflux with heating for 6 hours. Methanol was removed from the reaction solution, water was added, and 3N aqueous hydrochloric acid was added until the pH was 1. The reaction was transferred to a separatory funnel and washed with 1: 1, 30mL of solution was extracted 5 times. The extracted organic layer was collected, dehydrated with anhydrous sodium sulfate, and then distilled off the solvent with an evaporator to obtain a solid. The reaction was repeated to give the analytically required amount of solid.
Purity of 96.0% by high performance liquid chromatography, endothermic peak top temperature of 214 ℃ by differential scanning calorimetry, and loose bulk density of 0.12g/cm3。
A graph showing differential scanning calorimetry data is shown in FIG. 4 (sample amount: 2.131 mg).
< comparative example 2 >
4.0g of compound b, 34.8g of potassium carbonate, 20.1g of bromoacetic acid and 118mL of methanol were placed in a four-necked flask, and the mixture was reacted under reflux with heating for 6 hours. Methanol was removed from the reaction solution, water was added, and 3N aqueous hydrochloric acid was added until the pH was 1. To the precipitated solid was added 1: 1 was filtered without dissolving, but 150mL of the solution was obtained as a solid. The reaction was repeated to give the analytically required amount of solid.
Purity of 98.3% by high performance liquid chromatography, endothermic peak top temperature of 210 ℃ by differential scanning calorimetry, and loose bulk density of 0.14g/cm3。
A graph showing differential scanning calorimetry data is shown in FIG. 5 (sample amount: 2.536 mg).
< comparative example 3 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A20g and methyl ethyl ketone 158.3g were charged into a four-necked flask, and the temperature was raised to 79 ℃ to dissolve the compound, and then the flask was cooled at a cooling rate of 10 ℃ per hour to confirm the deposition of crystals at 44 ℃. Then, the crystallized liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 11.2g of the crystal of the present invention.
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.23g/cm3The hue (APHA) was 30. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.8, 16.3, 18.2, 22.5, 23.4, 24.4, 26.8, 36.3.
< comparative example 4 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A15g and 237.1g of butyl acetate were placed in a four-necked flask, and the temperature was raised to 125 ℃ to dissolve the compound, followed by cooling at a cooling rate of 10 ℃ per hour to confirm the precipitation of crystals at 110 ℃. Then, the crystallized liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 13.0g of the crystal of the present invention.
Purity of 99.9% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.18g/cm3The hue (APHA) was 30. In addition, XRDIs 9.2, 14.8, 16.1, 18.2, 22.5, 23.3, 24.3, 26.8, 36.3.
< comparative example 5 >
Using the compound a obtained in example 2, a crystallization step was performed in a nitrogen atmosphere. Compound A10g and 210.1g of cyclopentyl methyl ether were charged into a four-necked flask, and the temperature was raised to 103 ℃ to dissolve the compound, followed by cooling at a cooling rate of 10 ℃ per hour to confirm the precipitation of crystals at 60 ℃. Then, the crystallization liquid was cooled to 25 ℃, filtered, and then dried under reduced pressure to obtain 6.5g of the crystal of the present invention.
Purity of 99.2% by high performance liquid chromatography, endothermic peak top temperature of 215 ℃ by differential scanning calorimetry, and loose bulk density of 0.23g/cm3The hue (APHA) was 90. In addition, XRD is characterized by a2 theta (deg) of 9.2, 14.7, 16.2, 18.2, 22.5, 23.4, 24.3, 26.8, 36.3.
Claims (4)
1. A crystal of 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl characterized by having an endothermic peak top temperature of 215 to 220 ℃ as measured by differential scanning calorimetry and a loose bulk density of 0.3 to 0.6g/cm3The range of (1).
2. The crystalline 2,2 '-bis (carboxymethoxy) -1, 1' -binaphthyl of claim 1, wherein a 30% by weight solution of the crystalline in tetrahydrofuran has a Hazen color APHA of 100 or less.
3. A method for producing a crystal according to claim 1 or 2, characterized in that crystallization is carried out using any one of the following solvents (1) to (5):
(1) one or more selected from chain ketone solvents having a total carbon number of 5 to 8,
(2) one or more cyclic ketone solvents having 5 to 8 total carbon atoms,
(3) at least one selected from cyclic ether solvents having 4 to 8 total carbon atoms,
(4) one or more cyclic ester solvents having 4 to 8 total carbon atoms,
(5) more than one kind of chain ketone solvent with 3-8 total carbon atoms and water.
4. The production method according to claim 3, wherein the crystallization is performed by any one of the following solvents (1 ') to (5'):
(1') methyl isobutyl ketone or 2-octanone,
(2') a cyclohexanone (a) and (b),
(3') tetrahydrofuran or 1, 4-dioxane,
(4') gamma-butyrolactone or gamma-valerolactone,
(5') a mixed solvent of acetone and water or a mixed solvent of methyl ethyl ketone and water.
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| JP2019085666A JP7295692B2 (en) | 2018-05-31 | 2019-04-26 | Crystalline form of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl |
| JP2019-085666 | 2019-04-26 | ||
| PCT/JP2019/021005 WO2019230685A1 (en) | 2018-05-31 | 2019-05-28 | Crystal of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl |
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| CN106170469A (en) * | 2014-03-10 | 2016-11-30 | 田冈化学工业株式会社 | The crystalline polymorph of 2,2 ' double (2 hydroxyl-oxethyl) 1,1 ' dinaphthalene and manufacture method thereof |
| CN105541605A (en) * | 2016-02-04 | 2016-05-04 | 扬州大学 | Synthesis method of axially chiral dinaphthalene ligand precursor (s)-2,2'-dinaphthyl-1,1'-dicarboxylic acid |
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| CARMINE COLUCCINI等: "《Locked chromophores as CD and NMR probes for the helical conformation of tetraamidic macrocycles》" * |
| JAMIE BICKLEY等: "《Dirhodium(II) carboxylate complexes as building blocks. cis-Chelating dicarboxylic acids designed to bridge the dinuclear core》" * |
| JEAN-MARIE LEHN等: "《Synthesis and properties of chiral macrotricyclic ligands. Complexation and transport of chiral molecular cations and anions》" * |
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