DIHYDRATE OF BENZOTHIOPHENE COMPOUND OR OF A SALT THEREOF, AND PROCESS FOR PRODUCING THE SAME
20230049327 · 2023-02-16
Assignee
Inventors
- Hiroshi YAMASHITA (Osaka, JP)
- Tetsuya SATO (Osaka, JP)
- Takuya MINOWA (Osaka, JP)
- Yusuke HOSHIKA (Osaka, JP)
- Hidekazu TOYOFUKU (Osaka, JP)
- Tatsuya YAMAGUCHI (Osaka, JP)
- Masahiro SOTA (Osaka, JP)
- Shuuji KAWANO (Osaka, JP)
- Takayuki NAKAMURA (Osaka, JP)
- Ryohei ETO (Osaka, JP)
- Takuma IKEBUCHI (Osaka, JP)
- Kei MORIYAMA (Osaka, JP)
- Nobuaki ITO (Osaka, JP)
Cpc classification
C07D409/12
CHEMISTRY; METALLURGY
A61K9/0019
HUMAN NECESSITIES
A61P25/28
HUMAN NECESSITIES
A61P25/18
HUMAN NECESSITIES
International classification
Abstract
An object of the present invention is to provide a compound that can be used as a more superior therapeutic agent for central nervous system diseases. The present invention provides a dihydrate of 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one or of a salt thereof, and a process for producing the same
Claims
1. A dihydrate of 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one or of a salt thereof.
2. A method for preventing and/or treating a central nervous system disease comprising a dihydrate of 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one or of a salt thereof as an active ingredient.
3. The method according to claim 2 which is for preventing or treating a central nervous system disease selected from the group consisting of schizophrenia, treatment-resistant, refractory and chronic schizophrenia, emotional disturbance, psychotic disorder, mood disorder, bipolar disorder, mania, depression, endogenous depression, major depression, melancholic and treatment-resistant depression, dysthymic disorder, cyclothymic disorder, anxiety disorder, somatoform disorder, factitious disorder, dissociative disorder, sexual disorder, eating disorder, sleep disorder, adjustment disorder, substance-related disorder, anhedonia, delirium, cognitive impairment, cognitive impairment associated with Alzheimer’s disease, Parkinson’s disease, and other neurodegenerative diseases, BPSD caused by cognitive impairment, cognitive impairment in schizophrenia, cognitive impairment caused by treatment-resistant, refractory or chronic schizophrenia, vomiting, motion sickness, obesity, migraine, pain, mental retardation, autism, Tourette’s syndrome, tic disorder, attention deficit hyperactivity disorder, conduct disorder, and Down’s syndrome.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
Examples
[0148] The present invention is described in further detail with reference to Examples and Test Examples. However, the scope of the invention is not limited to these Examples.
Reference Example 1: Synthesis of 7-(4-Chlorobutoxy)-1H-Quinolin-2-One
[0149] Methanol (149 L), 7-hydroxy-1H-quinolin-2-one (14.87 kg), and potassium hydroxide (6.21 kg) were mixed and stirred. After dissolution, 1-bromo-4-chlorobutane (47.46 kg) was further added thereto and the resulting mixture was stirred under reflux for seven hours. Thereafter, the mixture was stirred at 10° C. for one hour. The precipitated crystal was centrifuged and washed with methanol (15 L). The wet crystal was collected and placed in a tank. Water (149 L) was added thereto, followed by stirring at room temperature. After centrifugation, the resulting solid was washed with water (30 L). The wet crystal was collected and placed in a tank. After adding methanol (74 L), the mixture was stirred under reflux for one hour, cooled to 10° C., and then stirred. The precipitated crystal was centrifuged and washed with methanol (15 L). The separated crystal was dried at 60° C. to obtain 7-(4-chlorobutoxy)-1H-quinolin-2-one (15.07 kg).
Reference Example 2: Synthesis of 7-[4-(4-Benzo[b]Thiophen-4-yl-Piperazin-1-yl)Butoxy]-1H-Quinolin-2-One
[0150] Water (20 L), potassium carbonate (1.84 kg), 1-benzo[b]thiophen-4-yl-piperazine hydrochloride (3.12 kg), and ethanol (8 L) were mixed and stirred at 50° C. 7-(4-Chlorobutoxy)-1H-quinolin-2-one (2.80 kg) obtained in Reference Example 1 was added to the mixture and stirred under reflux for nine hours. After concentrating the solvent (8 L) under ordinary pressure, the mixture was stirred at 90° C. for one hour and then cooled to 9° C. The precipitated crystal was centrifuged and then sequentially washed with water (8 L) and ethanol (6 L). The separated crystal was dried at 60° C. to obtain a crude product. The crude product (4.82 kg) and ethanol (96 L) were mixed in a reaction vessel, and acetic acid (4.8 L) was introduced into the reaction vessel. The mixture was stirred under reflux for one hour to dissolve the crude product. After introducing hydrochloric acid (1.29 kg), the mixture was cooled to 10° C. The mixture was heated again, refluxed for one hour, and cooled to 7° C. The precipitated crystal was centrifuged and washed with ethanol (4.8 L). The separated crystal was dried at 60° C. to obtain 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one hydrochloride (5.09 kg). The resulting 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one hydrochloride (5.00 kg), ethanol (45 L), and water (30 L) were mixed in a reaction vessel. The mixture was stirred under reflux to dissolve the 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one hydrochloride. Activated carbon (500 g) and water (5 L) were added thereto, and an activated carbon treatment was conducted under reflux for 30 minutes. After performing hot filtration, a solution containing sodium hydroxide (511 g) dissolved in water (1.5 L) was flowed into the reaction vessel while stirring the filtrate under reflux. After stirring under reflux for 30 minutes, water (10 L) was introduced thereto and the mixture was cooled to approximately 40° C. The precipitated crystal was centrifuged and washed with water (125 L). The separated crystal was dried at 80° C. to obtain 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (3.76 kg).
Example 1: Preparation of 7-[4-(4-Benzo[b]Thiophen-4-yl-Piperazin-1-yl)Butoxy]-1H-Quinolin-2-One Dihydrate
[0151] The 7-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (3.2 kg) obtained in Reference Example 2, ethanol (64 L), water (74 L), and acetic acid (1.77 kg) were mixed in a reaction vessel to prepare an acidic liquid mixture. The mixture was stirred under reflux to dissolve the 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (reflux temperature: 84° C.). After cooling to -5° C., the solution obtained above was introduced, over a period of 30 minutes, into a solution containing 25% sodium hydroxide (5.9 kg) and water (54 L) that was cooled to 0° C., to prepare a liquid mixture with pH10. After being stirred at 5° C. or below for one hour, the mixture was heated to 20 to 30° C. and further stirred for seven hours. The precipitated crystal was filtered and washing with water (320 L) was performed until alkali in the solid component disappeared (i.e., until the pH value of the filtrate became 7). The solid component was then air-dried until its weight became constant to obtain a white solid 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one dihydrate (unground, 3.21 kg).
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[0153] The X-ray powder diffraction spectrum of the dihydrate prepared by the aforesaid method was measured using an X-ray diffractometer (D8 ADVANCE, available from Bruker AXS).
[0154] The IR (KBr) spectrum of the dihydrate prepared by the aforesaid method was measured.
[0155] The Raman spectrum of the dihydrate prepared by the aforesaid method was measured.
[0156] Other than those mentioned above, absorption was also observed in the vicinity of wavenumbers 1656 cm.sup.-1, 1613 cm.sup.-1, 1563 cm.sup.-1, 1512 cm.sup.-1, 1468 cm.sup.-1, 1446 cm.sup.-1, 1241 cm.sup.-1, 1203 cm.sup.-1, 1145 cm.sup.-1, 1096 cm.sup.-1, 1070 cm.sup.-1, 971 cm.sup.-1, and 822 cm.sup.-1.
[0157] The water content of the dihydrate prepared by the aforesaid method was measured using a moisture meter (CA-100, available from Mitsubishi Chemical Analytech Co., Ltd.) by the Karl Fischer method. As a result, the dihydrate had a water content of 7.79% by weight.
Example 2: Preparation of Finely Ground Dihydrate
[0158] Dihydrate crystal (2.73 kg) obtained in Example 1 was ground using a jet mill. Here, the air pressure was set at 5 kgf/cm.sup.2, and the rotational speed of the feeder was set at 20 rpm. As a result, finely ground 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one dihydrate (2.61 kg, 95.6%) was obtained.
[0159] The dihydrate (finely ground product) thus obtained had a mean particle diameter of 5.5 .Math.m. The mean particle diameter was measured using a Microtrack HRA, manufactured by Nikkiso Co., Ltd.
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[0161] The X-ray powder diffraction spectrum of the dihydrate prepared by the aforesaid method was measured in the same manner as in Example 1.
[0162] Other than those mentioned above, the diffraction peaks were also observed at 2θ = 6.8°, 12.2°, 14.0°, 14.5°, 17.4°, 18.1°, 18.5°, 19.0°, 19.2°, 19.6°, 20.3°, 20.6°, 21.5°, 22.7°, 23.4°, 25.0°, 26.1°, 27.1°, 28.6°, 29.0°, 30.4°, 34.0°, 34.5°, 35.3°, and 36.7°.
[0163] The IR (KBr) spectrum of the dihydrate prepared by the aforesaid method was measured in the same manner as in Example 1.
[0164] The Raman spectrum of the dihydrate prepared by the aforesaid method was measured.
[0165] Other than those mentioned above, absorption was also observed in the vicinity of wavenumbers 1656 cm.sup.-1, 1614 cm.sup.-1, 1563 cm.sup.-1, 1512 cm.sup.-1, 1467 cm.sup.-1, 1446 cm.sup.-1, 1241 cm.sup.-1, 1203 cm.sup.-1, 1145 cm.sup.-1, 1095 cm.sup.-1, 1069 cm.sup.-1, 971 cm.sup.-1, and 822 cm.sup.-1.
[0166] The water content of the dihydrate prepared by the aforesaid method was measured using a moisture meter (CA-100, available from Mitsubishi Chemical Analytech Co., Ltd.) by the Karl Fischer method. As a result, the dihydrate had a water content of 6.74% by weight.
Example 3: Preparation of 7-[4-(4-Benzo[b]Thiophen-4-yl-Piperazin-1-yl)Butoxy]-1H-Quinolin-2-One Dihydrate
[0167] 7-(4-Benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (5.0 kg), ethanol (100 L), water (115 L), and DL-lactic acid (2.29 kg) were mixed to prepare an acidic liquid mixture. The liquid mixture was stirred under reflux to dissolve the 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (reflux temperature: 82° C.). After cooling to -5° C., the solution obtained above was introduced, over a period of about 15 minutes, into a solution containing sodium hydroxide (1.48 kg) and water (135 L) that was cooled to 1° C., to prepare a liquid mixture with pH11. After being stirred at approximately 2 to 5° C. for three hours, the mixture was heated to 45° C. and further stirred at 45 to 50° C. for two hours. The precipitated crystal was filtered and washing with water (200 L) was performed until alkali in the solid component disappeared (i.e., until the pH value of the filtrate became 7). The solid component was further washed with a liquid mixture of ethanol (15 L) and water (20 L). The solid component was then dried at room temperature until its weight became constant to obtain a white solid 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one dihydrate (unground, 5.11 kg).
[0168] The dihydrate thus obtained was the same as that obtained in Example 1.
[0169] The Raman spectrum of the dihydrate prepared by the aforesaid method was measured.
[0170] Other than those mentioned above, absorption was also observed in the vicinity of wavenumbers 1656 cm.sup.-1, 1614 cm.sup.-1, 1563 cm.sup.-1, 1512 cm.sup.-1, 1468 cm.sup.-1, 1446 cm.sup.-1, 1241 cm.sup.-1, 1203 cm.sup.-1, 1145 cm.sup.-1, 1126 cm.sup.-1, 1096 cm.sup.-1, 1070 cm.sup.-1, 972 cm.sup.-1, and 822 cm.sup.-1.
Reference Example 3
[0171] 7-(4-Benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one anhydride (7 g), ethanol (140 mL), water (161 mL), and lactic acid (2.7 mL) were mixed in a reaction vessel. The mixture was heated to reflux while being stirred to dissolve the 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one anhydride. After being cooled to approximately -10° C., the solution obtained above was introduced, while being stirred, into a solution containing sodium hydroxide (2.1 g) and water (189 mL) that was cooled to approximately 0° C. After being stirred at a temperature of approximately 0° C. for 3 hours, solid-liquid separation was performed.
[0172] The X-ray powder diffraction spectrum of the hydrate prepared by the aforesaid method was measured in the same manner as in Example 1.
Comparative Example 1: Preparation of 7-[4-(4-Benzo[b]Thiophen-4-yl-Piperazin-1-yl)Butoxy]-1H-Quinolin-2-One Anhydride
[0173] The 7-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one (700 g) prepared in Reference Example 2, ethanol (14 L), and acetic acid (1.4 L) were mixed in a reaction vessel. The mixture was heated to the reflux temperature (76° C.) to dissolve 7-[4-(4-benzo [b] thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one. Concentrated hydrochloric acid (158 mL) was further added thereto and then cooled to 10° C. while being stirred. Thereafter, the mixture was heated again, stirred under reflux for one hour, and then cooled to 8° C. The precipitated solid was filtered by suction and washed with ethanol (0.7 L). The solid component was then dried at 60° C. until its weight became constant to obtain a white solid 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one hydrochloride (814 g). 7-[4-(4-Benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one hydrochloride (800 g), ethanol (7.2 L), and water (4.8 L) were mixed in a reaction vessel, and the mixture was heated to the reflux temperature (80° C.) while being stirred. After performing hot filtration, the mixture was heated again to 78° C., and the crystal precipitated in the filtrate was dissolved. A solution containing sodium hydroxide (81.6 g) dissolved in water (240 mL) was flowed into the above-obtained solution and the mixture was stirred under reflux for 30 minutes. Water (2.4 L) was added to the mixture, followed by cooling to 40° C. while being stirred. The precipitated solid was filtered and washed with water (16 L). The solid was dried at 80° C. to obtain a white solid 7-[4-(4-benzo[b]thiophen-4-yl-piperazin-1-yl)butoxy]-1H-quinolin-2-one anhydride (637 g).
[0174] The 1H-NMR spectrum of the anhydride obtained above was measured in the same manner as in Example 1.
[0175] The X-ray powder diffraction spectrum of the anhydride obtained above was measured in the same manner as in Example 1.
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[0177] The IR (KBr) spectrum of the anhydride obtained above was measured in the same manner as in Example 2.
[0178] The water content of the anhydride prepared by the aforesaid method was measured in the same manner as in Example 2. The result revealed that the anhydride that was obtained had a water content of 0.04% by weight.
Test Example 1: Measurement of Drug Residue in Muscle
[0179] The dihydrate of the present invention (150 mg) was dispersed to the suspension medium (1 mL) described below, and pulverized using 5 mm zirconia beads (1.2 g, pulverization time: 30 min) while being stirred with a stirrer. The suspension medium used for pulverization was a solution containing 0.832% (w/v) sodium carboxymethylcellulose (CMC-Na), 4.16% (w/v) mannitol, and 0.074% (w/v) sodium dihydrogenphosphate monohydrate. The pH thereof was adjusted to 7.0 by adding an appropriate amount of sodium hydroxide. The concentration of each preparation was adjusted to 100 mg/mL using this medium.
[0180] The dihydrate (finely ground product) thus obtained had a mean particle diameter of 3.5 .Math.m. An anhydride was subjected to pulverization in the same manner to obtain an anhydride (finely ground product) having a mean particle diameter of 3.5 .Math.m. The mean particle diameter was measured using a laser diffraction particle size analyzer (SALD-3000J or SALD-3100, manufactured by Shimadzu Corporation).
[0181] Injectable preparations each containing the dihydrate of the present invention (finely ground product, mean particle diameter: 3.5 .Math.m) or an anhydride (finely ground product, mean particle diameter: 3.5 .Math.m) were obtained by the procedure described above. Table 1 shows the formulations thereof.
[0182] Each injectable preparation thus obtained was intramuscularly injected into a rat in a dosage of 25 mg/kg. Each injectable preparation was injected into three rats. 56 days after the injection, the rats were dissected, and the number of rats exhibiting drug residue in muscle was counted. Table 2 shows the results.
TABLE-US-00001 Formulations Active ingredient 100 mg Sodium carboxymethylcellulose 8.32 mg Mannitol 41.6 mg Sodium dihydrogenphosphate monohydrate 0.74 mg Sodium hydroxide Q.S. (adjusted to pH7) Distilled water Q.S. Total 1 mL
TABLE-US-00002 Active ingredient The number having residue in muscle (Number having residue/Total) Dihydrate 3/3 Anhydride 0/3
Test Example 2: Pharmacokinetics Test Using a Dog
[0183] Injectable preparations containing the dihydrate of the present invention as an active ingredient were formulated as shown in Table 3. Each of the injectable preparations was injected into the thigh muscle of a dog in such a dosage that 10 mg/kg of active ingredient calculated as the anhydride of the present invention was contained.
[0183] TABLE-US-00003 Test Example 2 Component Amount (mg) Dihydrate of the present invention 108 Sorbitol 50 Sodium carboxymethylcellulose 10 Sodium dihydrogenphosphate dihydrate 0.78 Benzyl benzoate 1 Polysorbate 80 2 Sodium hydroxide Q.S. (pH 7.0) Injection water Q.S. Total 1 mL